Substituted quinolines and cinnolines

ABSTRACT

The compounds of the formula: ##STR1## where the substituents are herein below defined, are fungicides, insecticides, and miticides.

RELATED APPLICATIONS

This application is a division of application Ser. No. 07/324,058, filed Mar. 16, 1989, now U.S. Pat. No. 5,114,939, which in turn is a continuation-in-part of application Ser. No. 150,366, filed Jan. 29, 1988, now abandoned.

BACKGROUND OF THE INVENTION Field of the Invention

This invention provides new compounds that have excellent plant fungicide activity. Some of the compounds have also demonstrated insecticidal and miticidal activity. The invention also provides compositions and combination products that contain a compound of the invention as active ingredient. The invention also provides fungicidal, miticidal, and insecticidal methods.

There is an acute need for new fungicides, insecticides, and miticides, because target pathogens are rapidly developing resistance to currently used pesticides. Widespread failure of N-substituted azole fungicides to control barley mildew was observed in 1983, and has been attributed to the development of resistance. At least 50 species of fungi have developed resistance to the benzimidazole fungicides. The field performance of DMI (demethylation inhibitor) fungicides, which are now widely relied on to protect cereal crops from powdery mildew, has declined since they were introduced in the 1970's. Even recent fungicides, like the acylalanines, which initially exhibited excellent control of potato late blight and grape downy mildew in the field, have become less effective because of widespread resistance. Similarly, mites and insects are developing resistance to the miticides and insecticides in current use. Resistance to insecticides in arthropods is widespread, with at least 400 species resistant to one or more insecticides. The development of resistance to some of the older insecticides, such as DDT, the carbamates, and the organophosphates, is well known. But resistance has even developed to some of the newer pyrethroid insecticides and miticides. Therefore a need exists for new fungicides, insecticides, and miticides.

SUMMARY OF THE INVENTION

This invention provides compounds of the formula (1) ##STR2## wherein:

R¹ to R⁴ are independently

H, halo, (C₁ -C₄) alkyl, branched (C₃ -C₄) alkyl, halo (C₁ -C₄) alkyl, (C₁ -C₄) alkoxy, NO₂, or NH₂, at least two of R¹ to R⁴ being H,

or one of R² to R⁴ is --NR⁷ --Y--Ar or O--Y--Ar and the rest of R¹ to R⁴ are H;

W is N, or CR⁵ ;

R⁵ is H, CH₃, Cl, O--Y--Ar, or --NR⁷ --Y--Ar;

R⁶ is H, CH₃, Cl or Br;

A is --O--Alk or --X--Y--Ar;

Alk is a C₂ -C₁₈ saturated or unsaturated hydrocarbon chain, straight chain or branched, optionally substituted with halo, halo (C₁ -C₄) alkoxy, (C₃ -C₈) cycloalkyl, hydroxy, or acetyl;

X is O, NR⁷, or CR⁸ R⁹, provided that if one of R² to R⁵ is NR⁷ --Y--Ar or O--Y--Ar, then X--Y--Ar is an identical group;

R⁷ is H, (C₁ -C₄) alkyl, or acetyl;

R⁸ and R⁹ are independently H, (C₁ -C₄) alkyl, (C₁ -C₄) acyl, halo, or OH, or R⁸ and R⁹ combine to form a saturated or unsaturated carbocyclic ring comprising three to seven carbon atoms;

Y is an alkylene chain 2 to 8 carbon atoms long, that optionally includes an O, S, SO, SO₂, or NR⁷ group, and optionally includes a saturated or unsaturated carbocyclic ring comprising three to seven carbon atoms, and optionally is substituted with (C₁ -C₃) alkyl, (C₂ -C₄) alkenyl, phenyl, (C₃ -C₈) cycloalkyl, hydroxy, halo, or (C₁ -C₄) acyl; and

Ar is

1,3-benzodioxolyl

fluorenyl,

pyridyl

substituted pyridyl,

indolyl,

furanyl,

substituted furanyl,

thienyl, optionally substituted with CH₃ or Cl,

thiazolyl,

cyclopentyl,

1-methylcyclopentyl,

cyclohexenyl (tetrahydrophenyl),

cyclohexyl (hexahydrophenyl),

naphthyl,

substituted naphthyl,

dihydronaphthyl,

tetrahydronaphthyl,

decahydronaphthyl, or

a group of the formula (2): ##STR3## where

R¹⁰ to R¹⁴ are independently H, halo, I, (C₁ -C₁₀) alkyl, branched (C₃ -C₆) alkyl, halo (C₁ -C₇) alkyl, (C₁ -C₇) alkoxy, halo (C₁ -C₇) alkoxy, phenoxy, substituted phenoxy, phenylthio, substituted phenylthio, phenyl, substituted phenyl, NO₂ NH₂, acetoxy, OH, CN, SiR¹⁵ R¹⁶ R¹⁷, or OSiR¹⁵ R¹⁶ R¹⁷, where R¹⁵, R¹⁶, and R¹⁷ are independently (C₁ -C₄) alkyl or (C₃ -C₄) branched alkyl, phenyl, or substituted phenyl, provided that unless each of R¹⁰ to R¹⁴ is F, CH₃, or H, then at least two of R¹⁰ to R¹⁴ are H;

or an acid addition salt of a compound of formula (1) or an N-oxide of a compound of formula (1) when W is CR⁵

provided that the following compounds are excluded:

1) N-[4-(4-chlorophenyl)butyl]-7-chloro-4-quinolinamine;

2) N-(2-phenylethyl)-4-quinolinamine.

The final proviso excludes compounds that are known per se or that could be considered similar to known compounds.

The fungicidal combinations of the invention comprise at least 1% by weight of a compound of formula (1), or N- [4-(4-chlorophenyl)butyl]-7-chloro-4-quinolineamine or N-(2-phenylethyl)-4-quinolinamine, in combination with a second fungicidal compound.

The fungicidal compositions of the invention comprise a disease inhibiting and phytologically acceptable amount of a compound of formula (1), or N-[4-(4-chlorophenyl)butyl]-7-chloro-4-quinolinamine, or N-(2-phenylethyl)-4-quinolinamine, in combination with a phytologically-acceptable carrier.

The fungicidal method of the invention comprises applying to the locus of a plant pathogen a disease inhibiting and phytologically acceptable amount of a compound of the formula (1), or N-[4-(4-chlorophenyl)butyl]-7-chloro-4-quinolinamine, or N-(2-phenylethyl)-4-quinolinamine.

The insecticidal or miticidal combinations of the invention comprise at least 1% by weight of a compound of formula (1) in combination with a second insecticide or miticide.

The insecticide or miticide compositions of the invention comprise an insect or mite inactivating amount of a compound of formula (1) in combination with a phytologically-acceptable carrier.

The insecticide and miticide methods of the invention comprise applying to a locus of an insect or mite an insect or mite inactivating amount of a compound of formula (1), or of a combination described above.

DETAILED DESCRIPTION OF THE INVENTION

Throughout this document, all temperatures are given in degrees Celsius, and all percentages are weight percentages unless otherwise stated.

The terms "(C₁ -C₃) alkyl", "(C₁ -C₄) alkyl", and "(C₁ -C₁₀) alkyl", when used alone, refer to straight chain alkyl radicals.

The terms "branched (C₃ -C₄) alkyl", and "branched (C₃ -C₆) alkyl" refer to all alkyl isomers containing the designated number of carbon atoms, excluding the straight chain isomers.

The terms "(C₁ -C₄) alkoxy" and "(C₁ -C₇) alkoxy" refer to straight or branched chain alkoxy groups.

The term "halo" used alone or in combination with other terms refers to F, Cl, or Br;

The term "halo (C₁ -C₇) alkyl" refers to a (C₁ -C₇) alkyl group, straight chain or branched, substituted with one or more halo groups.

The term "substituted phenyl" used alone or in combination with other terms, as in "substituted phenylthio" or "substituted phenylsulfonyl", refers to phenyl substituted with up to three groups selected from halo, I, (C₁ -C₁₀) alkyl, branched (C₃ -C₆) alkyl, halo (C₁ -C₇) alkyl, hydroxy (C₁ -C₇) alkyl, (C₁ -C₄) alkoxy, halo (C₁ -C₇) alkoxy, phenoxy, phenyl, NO₂, OH, CN, (C₁ -C₄) alkanoyloxy, or benzyloxy.

The term "substituted phenoxy" refers to phenoxy substituted with up to three groups selected from halo, I, (C₁ -C₁₀) alkyl, branched (C₃ -C₆) alkyl, halo (C₁ -C₇) alkyl, hydroxy (C₁ -C₇) alkyl, (C₁ -C₇) alkoxy, halo (C₁ -C₇) alkoxy, phenoxy, phenyl, NO₂, OH, CN, (C₁ -C₄) alkanoyloxy, or benzyloxy.

The terms "substituted naphthyl", "substituted pyridyl" and "substituted furanyl" refer to these ring systems substituted with halo, halo (C₁ -C₄) alkyl, CN, NO₂, (C₁ -C₄) alkyl, (C₃ -C₄) branched alkyl, phenyl, (C₁ -C₄) alkoxy, or halo (C₁ -C₄) alkoxy.

The term "unsaturated hydrocarbon chain" refers to a hydrocarbon chain containing one or two sites of unsaturation.

The term "HPLC" refers to high-performance liquid chromatography.

Compounds

While all of the compounds of the invention are useful fungicides, certain classes are preferred for reasons of greater efficacy or ease of synthesis, viz:

1. compounds of formula (1) where W is CR⁵ (i.e., substituted quinolines);

2. compounds of preferred class (1) where R⁵ is H;

3. compounds of formula (1) where R⁵ is H;

4. compounds of formula (1) where at least three of R¹ to R⁴ are H;

5. compounds of preferred class (4) where R⁴ is F (i.e., 8-fluoroquinolines);

6. compounds of preferred class (4) where R³ is F (i.e., 7-fluoroquinolines):

7. compounds of preferred class (4) where R³ is Cl (i.e., 7-chloroquinolines);

8. compounds of preferred class (4) where R² is F (i.e., 6-fluoroquinolines);

9. compounds of formula (1) where Y is an alkylene chain 2 to 4 carbon atoms long.

10. compounds of preferred class (9) where Y is --(CH₂)₂ --;

11. compounds of formula (1) where Ar is naphthyl;

12. compounds of formula (1) where Ar is thienyl;

13. compounds of formula (1) where Ar is thiazolyl;

14. compounds of formula (1) where Ar is cyclohexenyl;

15. compounds of formula (1) where Ar is a substituted phenyl group of formula (2);

16. compounds of preferred class (15) where at least three of R¹⁰ to R¹⁴ are H;

17. compounds of preferred class (15) where four of R¹⁰ to R¹⁴ are H;

18. compounds of preferred class (17) wherein one of R¹⁰ to R¹⁴ is Cl;

19. compounds of preferred class (18) where R¹² is Cl;

20. compounds of preferred class (17) wherein one of R¹⁰ is CF₃ ;

21. compounds of preferred class (17) wherein one of R¹⁰ to R¹⁴ is (C₁ -C₄) alkyl;

22. compounds of preferred class (21) wherein one of R¹⁰ to R¹⁴ is methyl;

23. compounds of preferred class (22) wherein R¹² is methyl;

24. compounds of preferred class (17) wherein one of R¹⁰ to R¹⁴ is branched (C₃ -C₆) alkyl;

25. compounds of preferred class (24) wherein R¹² is t-butyl;

26. compounds of preferred class (24) wherein R¹² is i-propyl;

27. compounds of preferred class (17) wherein one of R¹⁰ to R¹⁴ is phenyl or substituted phenyl;

28. compounds of preferred class (27) wherein R¹² is phenyl;

29. compounds of preferred class (17) wherein one of R¹⁰ to R¹⁴ is phenoxy or substituted phenoxy;

30. compounds of preferred class (29) wherein R¹² is phenoxy.

Compounds exhibiting particularly excellent activity against downy mildew include: 8-fluoro-N-(2-phenylethyl)-4-quinolinamine; 8-fluoro-N- [2-(4-phenyl-2-thiazolyl)ethyl]-4-quinolinamine; 8-fluoro-N-[2-[2-(trifluoromethyl)phenyl]ethyl]-4-quinolinamine; N-[2-(4-chlorophenyl)ethyl]-6-methyl-4-quinolinamine; 8-chloro-N-(2-phenylethyl)-4-quinolinamine; 8-fluoro-N-[2-(4-phenyl-2-thiazolyl)ethyl]-4-quinolinamine; 8-fluoro-N-[2-(2-naphthyl)ethyl-4-quinolinamine; 8-fluoro-N-[2-[3-(trifluoromethyl)phenyl]ethyl]-4-quinolinamine; 7-chloro-N-[2-(1-cyclohexenyl)ethyl]-4-quinolinamine; N-[2-[4-(1-methylethyl)phenyl]ethyl]-8-fluoro-4-quinolinamine; 8-fluoro-N-[2-(2-thienyl)ethyl]-4-quinolinamine; 4-[2-(3-chlorophenyl)ethoxy]-8-fluoroquinoline; 8-fluoro-4- [2-(3-(trifluoromethyl)phenyl)ethoxy]-quinoline; 4-[2-(4-methylphenyl)ethoxy]quinoline; 8-fluoro-4-[2-(4-methylphenyl)ethoxy]quinoline; and 4-[2-[4-(t-butyl)phenyl]ethoxy]-8-fluoroquinoline;

Compounds exhibiting particularly excellent activity against rice blast include: N-[2-(4-chlorophenyl)ethyl]-N-(8-fluoro-4-quinolinyl)acetamide; N-[2-[4-(i-propyl)-phenyl]ethyl]-8-fluoro-4-quinolinamine; 8-fluoro-N-(2-phenylethyl)-4-quinolinamine; N-[2-[4-(t-butyl)phenyl]ethyl-8-fluoro-4-quinolinamine; 8-fluoro-N-[2-(1,1'-biphenyl)-4-yl-ethoxy]quinoline; 8-fluoro-4-[2-(3-(trifluoromethyl)phenyl)ethoxy]quinoline; 8-fluoro-4- [2-(2-naphthyl)ethoxy]quinoline; 8-fluoro-4-[2-(4-methylphenyl)ethoxy]quinoline; and 8-fluoro-4-[3-(4-(t-butyl)phenyl)propyl]quinoline;

Compounds exhibiting particularly excellent activity against a broad spectrum of plant pathogens include: 8-fluoro-N-[2-(3-phenoxyphenyl)ethyl]-4-quinolinamine; N- [2-[4-(i-propyl)phenyl]ethyl]-8-fluoro-4-quinolinamine; N-[2-(1,1'-biphenyl)-3-ylethyl]-8-fluoro-4-quinolinamine; N-[2-(2,4-dichlorophenyl)ethyl]-8-fluoro-4-quinolinamine; 8-fluoro-4-[3-(4-(t-butyl)phenyl)propyl]quinoline; 8-fluoro-4-[3-(4-(i-propyl)phenyl)propyl]quinoline; 8-fluoro-4-[2-(2-(trifluoromethyl)phenyl)ethoxy ]quinoline; 4-[2-(4-chlorophenyl)ethoxy]-8-fluoroquinoline; 4-[2-(4-methylphenyl)ethoxy]quinoline; 8-fluoro-4-[2-(4-methylphenyl)ethoxy]quinoline; 8-fluoro-4-(2-phenylethoxy)quinoline; 8-fluoro-4-[2-(3-methylphenyl)ethoxy]quinoline; 8-fluoro-4-[2-(2-fluorophenyl)ethoxy]quinoline; 8-fluoro-4-[2-(2-methoxyphenyl)ethoxy]quinoline; and 8-fluoro-4-[2-(4-(i-propyl)phenyl)ethoxy]quinoline;

Compounds exhibiting particularly excellent activity as miticides include: 8-fluoro-N-[2-(4-iodophenyl)ethyl]-4-quinolinamine; N-[2-(4-bromophenyl)ethyl]-8-fluoro-4-quinolinamine; N-[2-(4-chlorophenyl)ethyl)-8-fluoro-4-quinolinamine; N-[2-(4-chlorophenyl)ethyl]-N-ethyl-8-fluoro-4-quinolinamine; N-3-(1,1'-biphenyl)-4-ylpropyl]-8-fluoro-4-quinolinamine; 8-fluoro-N-[2-(4-phenoxyphenyl)ethyl]-4-quinolinamine; N-[2-[4-(t-butyl)phenyl]ethyl]-8-fluoro-4-quinolinamine; N- [2-4-(i-propyl)phenyl]ethyl]-8-fluoro-4-quinolinamine; N-2-(4-chlorophenyl)ethyl]-6-fluoro-4-quinolinamine; 8-fluoro-N-[2-(1,1'-biphenyl)-4-yl-ethoxy]quinoline; 4-[2-(3-chlorophenyl)ethoxy]-8-fluoroquinoline; 4-[2-[4-(t-butyl)phenyl]ethoxy]-8-fluoroquinoline; 8-fluoro-4-[2-(4-(i-propyl)phenyl)ethoxy]quinoline; 8-fluoro-4-2-(3-(trifluoromethyl)phenyl)ethoxy]-quinoline; 8-fluoro-4-2-(4-methoxyphenyl)ethoxy]quinoline; 8-fluoro-4-[2-(3-phenoxyphenyl)ethoxy]quinoline; 8-fluoro-4-[2-(2-naphthyl)ethoxy]quinoline; 8-fluoro-4-[2-(1,1'-biphenyl)-2-yl-ethoxy]quinoline; 7-chloro-4 -[2-(1,1'-biphenyl)-4-yl-ethoxy]quinoline; 7-chloro-4-[2-(4-(t-butyl)phenyl)ethoxy]quinoline; 4-[2-(4-(t-butyl)phenyl)ethoxy]-7-fluoroquinoline; 4-[2-(1,1'-biphenyl)-4-ylethoxy]-7-fluoroquinoline; 8-fluoro-4-(3-phenylpropyl)quinoline; 8-fluoro-4-[3-(4-methylphenyl)propyl]quinoline; and 8-fluoro-4-[3-[3-(trifluoromethyl)phenyl]propyl]-quinoline.

Synthesis

The compounds of this invention are made using well known chemical procedures. The required starting materials are commercially available, or they are readily synthesized using standard procedures.

Synthesis of Compounds Wherein A is O--Y--Ar or --O--Alk

The compounds of formula (1) wherein A is O--Y--Ar or O--Alk were made by condensing a compound of formula (3): ##STR4## where R¹ to R⁴ are as previously defined, R⁶ ' is H or CH₃, and W' is N or CR⁵ ', where R⁵ ' is H, Cl, or CH₃, with an alcohol of the formula (4a or 4b):

    HO--Y--Ar                                                  (4a)

    HO--Alk                                                    (4b)

where

Y, Ar, and Alk are as previously defined.

The reaction is preferably carried out in the presence of a strong base, such as sodium hydride, in an inert organic solvent, such as DMF, at a temperature in the range of 0° to 25° C.

Synthesis of Compounds Wherein A is NR⁷ --Y--Ar

The compounds of formula (1) wherein A is NR⁷ --Y--Ar were prepared by condensing a compound of formula (3) with an amine of the formula (5) ##STR5## where

R⁷ is H or (C₁ -C₄) alkyl, and Y and

Ar are as previously defined. The chloride of formula (3) is allowed to react with an appropriate amine, preferrably at elevated temperature 100°-80° C.), and preferably in the presence of an acid acceptor, such as triethylamine. The reaction may be carried out neat, or in an inert organic solvent.

Compounds where R⁷ is acetyl were prepared by reacting amines of formula (1) where R⁷ is H, with an acylating agent, such as an acetyl chloride or acetic anhydride. In cases where the starting material of formula (3) is one wherein W' is CCl, a mixture of products is obtained, which are separable using HPLC.

Synthesis of Compounds Wherein A is CR⁸ R⁹ --Y--Ar

The compounds of formula (1) wherein A is CR⁸ R⁹ --Y--Ar can be made using the process described in J. Heterocyclic Chemistry, Vol. 14, p. 1081-1083 (1977) by A. Scoville and F. X. Smith. This process entails preparation of a 5-substituted-5-(4-quinolyl)barbituric acid of the formula (6) ##STR6## which is then hydrolyzed and decarboxylated by dissolving the intermediate in a solution of sodium hydroxide and water, refluxing, then making the solution slightly acidic with hydrochloric acid and again refluxing.

Derivatives

The compounds of formula (1) wherein R⁶ is Cl are prepared by halogenating a compound of formula (1) wherein R⁶ is H with POCl₃ /PCl₅.

The compounds of formula (1) wherein R⁶ is Br are prepared by reacting a compound of formula (1) wherein R⁶ is H with Br₂ in acetic acid.

N-oxides of the compounds of formula (1) are prepared by reacting the compound of formula (1) with an oxidizing agent, such as 3-chloroperoxybenzoic acid or hydrogen peroxide, in a non-reactive organic solvent, such as methylene chloride or chloroform, at -20° C. to room temperature, preferably at about 0° C.

The acid addition salts of compounds of formula (1) are obtained in the usual way.

Accordingly, the invention also provides a process for preparing a compound of formula (1) which comprises:

(a) condensing a compound of formula (3): ##STR7## where R¹ to R⁴ are as previously defined, R⁶ ' is H or CH₃, and W' is N or CR⁵ ', where R⁵ ' is H, Cl, or CH₃, with an alcohol of the formula (4a or 4b):

    HO--Y--Ar                                                  (4a)

    HO--Alk                                                    (4b)

where

Y, Ar, and Alk are as previously defined to provide a compound of formula (1) wherein A is O--Y--Ar or O--Alk; or

(b) condensing a compound of formula (3) with an amine of the formula (5) ##STR8## where

R⁷ is H or (C₁ -C₄) alkyl, and Y and

Ar are as previously defined to provide a compound of formula (1) wherein A is --NR⁷ --Y--Ar; or

(c) reacting an amine of formula (1) where R⁷ is H, with acetyl chloride or acetic anhydride to provide a compound of formula (1) wherein A is --NR⁷ --Y--Ar where R⁷ is acetyl; or

(d) hydrolyzing and decarboxylating a compound of the formula (6) ##STR9## to provide a compound of formula (1) wherein A is --CR⁸ R⁹ --Y--Ar; or

(e) halogenating a compound of formula (1) wherein R⁶ is H with POCl₃ /PCl₅ to provide a compound of formula (1) wherein R⁶ is Cl; or

(f) reacting a compound of formula (1) wherein R⁶ is H with Br₂ in acetic acid to provide a compound of formula (1) wherein R⁶ is Br; or

(g) oxidizing a compound of formula (1) wherein W is CR⁵ to provide the corresponding N-oxide.

Preparation of Quinoline Starting Materials

Quinoline starting materials can be synthesized using a variety of known procedures.

Organic Syntheses, collective volume 3, 1955, pp. 272-75, gives a procedure for preparing 4,7-dichloroquinoline, and other polysubstituted quinolines. Another general procedure is described in Tetrahedron, vol. 41, pp. 3033-36 (1985).

Many of the quinoline starting materials used in the following examples were prepared by the protocol shown in the following reaction scheme ##STR10## In cases where mixtures of isomeric products were obtained, the mixture of substituted 4-quinolones was chlorinated under standard conditions, and the 4-chloroquinolines were separated by liquid chromatography.

Preparation of Cinnoline Starting Materials

Cinnoline analogs are prepared via published methods. (C. M. Atkinson and J. C. Simpson - J. Chem. Soc. London, 1947, 232). The substituted 2-amino-acetophenone is diazotized at 0°-5° C. in water using sodium nitrite and mineral acid, and the intermediate diazonium salt is trapped by the enolic component of the ketone to provide the requisite 4-hydroxycinnoline. Routine chlorination provides the desired intermediates.

EXAMPLES 1 TO 328

Tables 1-12 identify compounds actually prepared by the above described general procedures, and give each compound's melting point. Specific illustrative preparations of the compounds of Examples 4, 10, 25, 69, 97, 154, 159, 173, 181, 186, 209, 212, 221, 238, 251, and 261 follow the table.

                  TABLE 1                                                          ______________________________________                                         N-(2-phenylethyl)-4-quinolinamines                                             EXAMPLE                                                                        NUMBER   COMPOUND              M.P.                                            ______________________________________                                         1        6-methoxy-N-(2-phenylethyl)-4-                                                                       NA                                                       quinolineamine                                                        2*       N-(2-phenylethyl)-4-quinolin-                                                                        159-160° C.                                       amine                                                                 3        6-ethyl-N-(2-phenylethyl)-4-                                                                         119-120° C.                                       quinolinamine                                                         4        N-ethyl-N-(2-phenylethyl)-4-                                                                         oil                                                      quinolinamine                                                         5        8-fluoro-N-(2-phenylethyl)-                                                                          149-150° C.                                       4-quinolinamine                                                       6        2-methyl-N-(2-phenylethyl)-                                                                          153-154° C.                                       4-quinolinamine                                                       7        6,8-difluoro-N-(2-phenyl-                                                                            196-197° C.                                       ethyl)-4-quinolinamine                                                8        7-fluoro-N-(2-phenylethyl)-                                                                          160-161° C.                                       4-quinolinamine                                                       9        6-fluoro-N-(2-phenylethyl)-                                                                          163-164° C.                                       4-quinolinamine                                                       10       N-[2-(4-chlorophenyl)ethyl]-                                                                         oil                                                      N-(8-fluoro-4-quinolinyl)-                                                     acetamide                                                             11       8-fluoro-N-[2-(4-iodo-                                                                               221-223° C.                                       phenyl)ethyl]-4-quinolin-                                                      amine                                                                 12       N-2-(4-bromophenyl)ethyl]-                                                                           235-238° C.                                       6,8-difluoro-4-quinolinamine                                          13       N-[2-(4-bromophenyl)ethyl]-                                                                          188-190° C.                                       8-(trifluoromethyl)-4-quinolin-                                                amine                                                                 14       N-[2-(4-chlorophenyl)ethyl]-                                                                         123-125° C.                                       6-methyl-4-quinolinamine                                              15       N-[2-(4-chlorophenyl)ethyl]-                                                                         113-115° C.                                       6,8-dimethyl-4-quinolinamine                                          16       N-[2-(4-chlorophenyl)ethyl]-                                                                         155-157° C.                                       6-methoxy-4-quinolinamine                                             17       N-(2-phenylethyl)-7-(tri-                                                                            138-139° C.                                       fluoromethyl)-4-quinolinamine                                         18       N-[2-(4-bromophenyl)ethyl]-                                                                          176-177° C.                                       4-quinolinamine                                                       19       N-[2-(4-methylphenyl)ethyl]-                                                                         159-160° C.                                       4-quinolinamine                                                       20*      N-[2-(4-chlorophenyl)ethyl]-                                                                         162-163° C.                                       4-quinolinamine                                                       21       N-(2-phenylpropyl)-4- 126-127°  C.                                      quinolinamine                                                         22       N-[2-(4-methoxyphenyl)-                                                                              127-128° C.                                       ethyl]-4-quinolinamine                                                23       N-(2,2-diphenylethyl)-4-                                                                             154-155° C.                                       quinolinamine                                                         24       N-(1-methyl-2-phenylethyl)-                                                                          132-133° C.                                       4-quinolinamine                                                       25       2-chloro-N-(2-phenylethyl)-                                                                          132-133° C.                                       4-quinolinamine                                                       26       α-[(4-quinolinylamino)-                                                                        195-197° C.                                       methyl]benzenemethanol                                                27       8-methyl-N-(2-phenylethyl)-                                                                          127-128° C.                                       4-quinolinamine                                                       28       6,8-dimethyl-N-(2-phenyl-                                                                            114-115° C.                                       ethyl)-4-quinolinamine                                                29       8-ethyl-N-(2-phenylethyl)-                                                                           98-99° C.                                         4-quinolinamine                                                       30       6-methyl-N-(2-phenylethyl)-                                                                          124-125° C.                                       4-quinolinamine                                                       31       7-chloro-N-(2-phenylethyl)-                                                                          137-138° C.                                       4-quinolinamine                                                       32       7,8-dimethyl-N-(2-phenyl-                                                                            183-185° C.                                       ethyl)-4-quinolinamine                                                33       8-chloro-N-(2-phenylethyl)-                                                                          156-157° C.                                       4-quinolinamine                                                       34       N-(2,2-diphenylpropyl)-4-                                                                            110-111° C.                                       quinolinamine                                                         35       N-[2-(4-fluorophenyl)ethyl]-                                                                         121-122° C.                                       4-quinolinamine                                                       36       8-fluoro-N-[2-(4-methoxy-                                                                            165-167° C.                                       phenyl)ethyl]-4-quinolinamine                                         37       7-chloro-N-[2-(4-chloro-                                                                             190-192° C.                                       phenyl)ethyl]-4-quinolinamine                                         38       N-[2-(3,4-dimethoxyphenyl)-                                                                          127-130° C.                                       ethyl]-8-fluoro-4-quinolin-                                                    amine                                                                 39       8-fluoro-N-[2-(3-phenoxy-                                                                            83-85° C.                                         phenyl)ethyl]-4-quinolin-                                                      amine                                                                 40       6,8-difluoro-N-(2-[1,1'-                                                                             216-218° C.                                       biphenyl]-4-ylethyl)-4-                                                        quinolinamine                                                         41       N-[2-(4-chlorophenyl)ethyl]-                                                                         218-220° C.                                       6,8-difluoro-4-quinolinamine                                          42       N-[2-(4-methoxyphenyl)ethyl]-                                                                        107-109° C.                                       7-(trifluoromethyl)-4-quinolin-                                                amine                                                                 43       7-chloro-N-[2-(3-methoxy-                                                                            155-158° C.                                       phenyl)ethyl]-4-quinolinamine                                         44       7-chloro-N-[2-(2,4-dichloro-                                                                         168-170° C.                                       phenyl)ethyl]-4-quinolinamine                                         45       7-chloro-N-[2-(3,5-di-                                                                               117-120° C.                                       methoxyphenyl)ethyl]-4-                                                        quinolinamine                                                         46       N-[2-(4-methoxyphenyl)-                                                                              120-123° C.                                       ethyl]-6-methyl-4-quinolin-                                                    amine                                                                 47       N-[2-(4-chlorophenyl)ethyl]-                                                                         153-155° C.                                       7-(trifluoromethyl)-4-quinolin-                                                amine                                                                 48       N-[2-(3,4-dimethoxyphenyl)-                                                                          oil                                                      ethyl]-7-(trifluoromethyl)-4-                                                  quinolinamine                                                         49       N-[2-(3-chlorophenoxy)ethyl]-                                                                        161-163° C.                                       8-fluoro-4-quinolinamine                                              50       7-chloro-N-[2-(4-methyl-                                                                             155-158° C.                                       phenyl)ethyl]-4-quinolinamine                                         51       8-chloro-N-[2-(4-fluoro-                                                                             194-196° C.                                       phenyl)ethyl]-4-quinolinamine                                         52       N-[2-(2,4-dichlorophenyl)-                                                                           158-160° C.                                       ethyl]-8-(trifluoromethyl)-4-                                                  quinolinamine                                                         53       N-[2-(2,4-dichlorophenyl)-                                                                           180-182° C.                                       ethyl]-6-methyl-4-quinolinamine                                       54       7-chloro-6-methoxy-2-methyl-                                                                         180-181° C.                                       N-(2-phenylethyl)-4-quinolin-                                                  amine                                                                 55       N-[2-(2-methoxyphenyl)-                                                                              127-128° C.                                       ethyl]-4-quinolinamine                                                56       N-[2-(4-chlorophenyl)ethyl]-                                                                         134-138° C.                                       6-fluoro-4-quinolinamine                                              57       N-[2-(4-chlorophenyl)ethyl]-                                                                         104-106° C.                                       2-methyl-6-fluoro-4-quinolin-                                                  amine                                                                 58       6-methyl-N-[2-(4-methyl-                                                                             122-124° C.                                       phenyl)ethyl]-4-quinolinamine                                         59       5,7-dichloro-N-[2-(4-chloro-                                                                         113-115° C.                                       phenyl)ethyl]-4-quinolinamine                                         60       7-chloro-N-[2-(3-phenoxy-                                                                            128-130° C.                                       phenyl)ethyl]-4-quinolinamine                                         61       8-methyl-N-[2-(4-chloro-                                                                             118-120° C.                                       phenyl)ethyl]-4-quinolinamine                                         62       8-fluoro-N-(2-cyclohexyl-2-                                                                          74-75° C.                                         phenyl)ethyl]-4-quinolinamine                                         63       8-fluoro-N-[2-(2-phenoxyphenyl)-                                                                     131-133° C.                                       ethyl]-4-quinolinamine                                                64       7,8-dimethyl-N-[2-(2-phenoxyphenyl)-                                                                 124-126° C.                                       ethyl]-4-quinolinamine                                                65       N-[2-(2,6-difluorophenyl)-                                                                           203-204° C.                                       ethyl]-8-fluoro-4-quinolin-                                                    amine                                                                 66       8-fluoro-N-[2-(3-fluoro-                                                                             174-175° C.                                       phenyl)ethyl]-4-quinolinamine                                         67       N-[2-(3,5-dimethoxyphenyl)-                                                                          122-123° C.                                       ethyl]-4-quinolinamine                                                68       8-fluoro-N-[2-(2-methoxy-                                                                            163-164° C.                                       phenyl)ethyl]-4-quinolinamine                                         69       3-chloro-N-(2-chloro-2-                                                                              oil                                                      phenyl)ethyl]-4-quinolinamine                                         70       N-(2-phenylethyl)-5,7-bis-                                                                           oil                                                      (trifluoromethyl)-4-quinolin-                                                  amine                                                                 71       8-fluoro-N-[2-(4-methyl-                                                                             176-177° C.                                       phenyl)ethyl]-4-quinolin-                                                      amine                                                                 72       N-[2-(1,1'-biphenyl)-3-ylethyl]-                                                                     140-142° C.                                       8-fluoro-4-quinolinamine                                              73       8-fluoro-4-[(2-phenylethyl)-                                                                         107-108° C.                                       amino]-3-quinolinemethanol                                            74       N-[2-(3-chlorophenyl)ethyl]-                                                                         191-192° C.                                       8-fluoro-4-quinolinamine                                              75       N-[2-(3,4-dichlorophenyl)-                                                                           204-206° C.                                       ethyl]-8-fluoro-4-quinolin-                                                    amine                                                                 76       N-[2-(2,4-dichlorophenyl)-                                                                           187-189° C.                                       ethyl]-8-fluoro-4-quinolin-                                                    amine                                                                 77       8-fluoro-N-(2-phenylpropyl)-                                                                         136-137° C.                                       4-quinolinamine                                                       78       8-fluoro-N-[2-(4-fluoro-                                                                             171-173° C.                                       phenyl)ethyl]-4-quinolinamine                                         79       N-[2-(4-chlorophenyl)-                                                                               126-127° C.                                       propyl]-8-fluoro-4-quinolin-                                                   amine                                                                 80       N-(2,2-diphenylpropyl)-8-                                                                            56-58° C.                                         fluoro-4-quinolinamine                                                81       8-fluoro-N-(2-phenylbutyl)-                                                                          114-116° C.                                       4-quinolinamine                                                       82       N-[2-(2-chlorophenyl)ethyl] -                                                                        175-177° C.                                       8-fluoro-4-quinolinamine                                              83       8-fluoro-N-[2-[4-(trifluoro-                                                                         205-206° C.                                       methyl)phenyl)ethyl]-4-                                                        quinolinamine                                                         84       7-chloro-N-[2-(4-methoxy-                                                                            122-124° C.                                       phenyl)ethyl]-4-quinolinamine                                         85       8-chloro-N-[2-(4-chloro-                                                                             185-187° C.                                       phenyl)ethyl]-4-quinolinamine                                         86       N-[2-(4-chlorophenyl)ethyl]-                                                                         192-194° C.                                       8-(trifluoromethyl)-4-quinolin-                                                amine                                                                 87       8-chloro-N-[2-(4-methyl-                                                                             184-186° C.                                       phenyl)ethyl]-4-quinolinamine                                         88       N-[2-(4-chlorophenyl)ethyl]-                                                                         177-179° C.                                       7,8-dimethyl-4-quinolinamine                                          89       8-fluoro-N-[2-(4-methyl-                                                                             153-154° C.                                       phenyl)ethyl]-4-quinolinamine                                         90       8-fluoro-N-[2-(4-phenoxy-                                                                            109-111° C.                                       phenyl)ethyl]-4-quinolin-                                                      amine                                                                 91       3-bromo-8-fluoro-N-(2-phenyl-                                                                        95-97° C.                                         ethyl)-4-quinolinamine                                                92       8-fluoro-N-(1-methyl-2-                                                                              166-168° C.                                       phenylethyl)-4-quinolinamine                                          93       2,8-dichloro-N-(2-phenyl-                                                                            190-192° C.                                       ethyl)-4-quinolinamine                                                94       N-[2-(4-bromophenyl)ethyl]-                                                                          198-199° C.                                       8-fluoro-4-quinolinamine                                              95       8-fluoro-N-[2-[3-(trifluoro-                                                                         161-162° C.                                       methyl)phenyl]ethyl]-4-                                                        quinolinamine                                                         96       N-[2-(4-chlorophenyl)ethyl)-                                                                         176-177° C.                                       8-fluoro-4-quinolinamine                                              97       8-fluoro-N-[2-[2-(trifluoro-                                                                         157-158° C.                                       methyl)phenyl]ethyl]-4-                                                        quinolinamine                                                         98       2-chloro-N-[2-(2,4-dichloro-                                                                         199-200° C.                                       phenyl)ethyl]-8-fluoro-4-                                                      quinolinamine                                                         99       N-(2-phenylethyl)-8-(tri-                                                                            151-152° C.                                       fluoromethyl)-4-quinolin-                                                      amine                                                                 100      7-chloro-N-[2-(2-methoxy-                                                                            140-142°                                          phenyl)ethyl]-4-quinolinamine                                         101      7-chloro-N-[2-(3,4-dichloro-                                                                         128- 130° C.                                      phenyl)ethyl]-4-quinolinamine                                         102      N-[2-(4-chlorophenyl)ethyl]-                                                                         176-178° C.                                       2-methyl-4-quinolinamine                                              103      N-[2-(2-chloro-6-fluoro-                                                                             198-201° C.                                       phenyl)ethyl]-8-fluoro-4-                                                      quinolinamine                                                         104      N-[2-(2,4-dichlorophenyl)-                                                                           175-177° C.                                       ethyl]-7-(trifluoromethyl)-                                                    4-quinolinamine                                                       105      N-[2-(4-chlorophenyl)ethyl]-                                                                         oil                                                      N-ethyl-8-fluoro-4-quinolin-                                                   amine                                                                 106      7-chloro-N-(4-fluorophenyl)-                                                                         83-85° C.                                         N-methyl-4-quinolinamine                                              107      7-chloro-N-[2-[3-(trifluoro-                                                                         184-186° C.                                       methyl)phenyl]ethyl]-4-                                                        quinolinamine                                                         108      N-[2-(3-bromophenyl)ethyl]-                                                                          206-208° C.                                       8-fluoro-4-quinolinamine                                              109      N-[2-(4-chlorophenyl)ethyl]-5,8-                                                                     oil                                                      dimethyl-4-quinolinamine                                              110      N(4)-[2-(4-chlorophenyl)ethyl]-                                                                      oil                                                      4,8-quinolinediamine                                                  111      N-[2-[4-( .sub.-t-butyl)phenyl]ethyl]-                                                               198-200° C.                                       8-fluoro-4-quinolinamine                                              112      N-[2-(2,3,4,5,6-tetramethyl-                                                                         204-207° C.                                       phenyl)ethyl]-8-fluoro-4-                                                      quinolinamine                                                         113      N-[2-(1,1-biphenyl)-4-yl-                                                                            178-180° C.                                       ethyl]-8-fluoro-4-quinolin-                                                    amine                                                                 114      N-[2-[4-( .sub.-i-propyl)phenyl]ethyl]-                                                              157-159° C.                              8-fluoro-4-quinolinamine                                                       115      N-[2-(2-chlorophenyl)ethyl]-                                                                         205-207° C.                                       8-chloro-4-quinolinamine                                              116      2-chloro-8-fluoro-N-(2-                                                                              158-159° C.                                       phenylethyl)-4-quinolinamine                                          117      8-fluoro-N-[2-(4-nitro-                                                                              234-236° C.                                       phenyl)ethyl]-4-quinolin-                                                      amine                                                                 118      N-[2-(2,6-dichlorophenyl)-                                                                           222-224° C.                                       ethyl]-8-fluoro-4-quinolin-                                                    amine                                                                 119      N-[2-(3,5-dimethoxyphenyl)-                                                                          131-132°  C.                                      ethyl]-8-fluoro-4-quinolin-                                                    amine                                                                 120      N-(2-phenylcyclopropyl)-4-                                                                           147-148° C.                                       quinolinamine                                                         121      N-[2-(4-chlorophenyl)ethyl]-N-                                                                       87-88° C.                                         (6-fluoro-4-quinolinyl)acetamide                                      122      N-[2-(4-methylphenyl)ethyl]-N-                                                                       97-98° C.                                         (6-methyl-4-quinolinyl)acetamide                                      123      8-fluoro-N-(2-phenylcyclopropyl)-4-                                                                  204-205° C.                                       quinolinamine                                                         124      N-[2-(4-chlorophenyl)ethyl]-N-(7-                                                                    oil                                                      chloro-4-quinolinyl)acetamide                                         125      N-(7-chloro-4-quinolinyl)-N-[2-(4-                                                                   oil                                                      methoxyphenyl)ethyl]acetamide                                         126      N-(7-chloro-4-quinolinyl)-N-[2-[3-                                                                   oil                                                      (trifluoromethyl)phenyl]ethyl]-                                                acetamide                                                             127      N-[2-(2,4-dichlorophenyl)ethyl]-N-                                                                   oil                                                      [7-(trifluoromethyl)-4-quinolinyl]-                                            acetamide                                                             128      N-[4-( .sub.-t-butyl)phenyl]ethyl-N-(8-                                                              126-128° C.                                       fluoro-4-quinolinyl)acetamide                                         129      N-[2-[4-( .sub.-i-propyl)phenyl]ethyl]-                                                              82-84° C.                                         N-(8-fluoro-4-quinolinyl)acetamide                                    130      N-[2-(1,1'-biphenyl)-4-ylethyl]-N-                                                                   oil                                                      (8-fluoro-4-quinolinyl)acetamide                                      131      N-[2-(pentamethylphenyl)ethyl]-N-                                                                    oil                                                      (8-fluoro-4-quinolinyl)acetamide                                      132      N-[2-(2-chlorophenyl)ethyl]-N-(8-                                                                    104-106° C.                                       chloro-4-quinolinyl)acetamide                                         133      N-[2-(4-methoxyphenyl)ethyl]-7,8-                                                                    183-185° C.                                       dimethyl-4-quinolinamine                                              ______________________________________                                          *not a compound claimed per se, but one used in the claimed compositions       and methods.                                                             

                  TABLE 2                                                          ______________________________________                                         N-(3-phenylpropyl)-4-quinolinamines                                            EXAMPLE                                                                        NUMBER   COMPOUND              M.P.                                            ______________________________________                                         134      7-chloro-N-[3-(1,1'-biphenyl)-4-                                                                     122-124° C.                                       ylpropyl]-4-quinolinamine                                             135      N-[3-(4-chlorophenyl)propyl]-8-                                                                      134-136° C.                                       fluoro-4-quinolinamine                                                136      N-[3-(4-chlorophenyl)propyl]-7-                                                                      177-179° C.                                       chloro-4-quinolinamine                                                137      N-[3-(1,1'-biphenyl)-4-ylpropyl]-                                                                    124-127° C.                                       8-fluoro-4-quinolinamine                                              138      8-fluoro-N-(1-methyl-3-phenylpropyl)-                                                                164-166° C.                                       4-quinolinamine                                                       139      N-(3-phenylpropyl)-4-quinolinamine                                                                   96-97° C.                                ______________________________________                                    

                  TABLE 3                                                          ______________________________________                                         N-(4-phenylbutyl)-4-quinolinamines                                             EXAMPLE                                                                        NUMBER    COMPOUND            M.P.                                             ______________________________________                                         140       8-fluoro-N-[4-(4-chlorophenyl)-                                                                    110-112° C.                                         butyl]-4-quinolinamine                                               141       N-[4-(4-chlorophenyl)butyl]-N-(8-                                                                  oil                                                        fluoro-4-quinolinyl)acetamide                                        ______________________________________                                    

                  TABLE 4                                                          ______________________________________                                         N-Arylalkyl-4-quinolinamines                                                   EXAMPLE                                                                        NUMBER   COMPOUND              M.P.                                            ______________________________________                                         142      N-[2-(1-cyclohexenyl)ethyl]-5,8-                                                                     78-81° C.                                         dimethyl-4-quinolinamine                                              143      N-[2-(1-cyclohexenyl)ethyl]-8-                                                                       153-155° C.                                       fluoro-4-quinolinamine                                                144      N-[2-(1-cyclohexenyl)ethyl]-6,8-                                                                     114-116° C.                                       dimethyl-4-quinolinamine                                              145      N-[2-(1-cyclohexenyl)ethyl]-6-                                                                       135-137° C.                                       ethyl-4-quinolinamine                                                 146      N-[2-(1-cyclohexenyl)ethyl]-N-                                                                       66-68° C.                                         (6-fluoro-4-quinolinyl)acetamide                                      147      N-[2-(2-thienyl)ethyl]-4-quinolin-                                                                   153-154° C.                                       amine                                                                 148      N-[2-(3-thienyl)ethyl]-4-quinolin-                                                                   156-157° C.                                       amine                                                                 149      6,8-difluoro-N-[2-(2-thienyl)ethyl]-                                                                 175-176° C.                                       4-quinolinamine                                                       150      6,8-difluoro-N-[2-(3-thienyl)ethyl]-                                                                 191-192° C.                                       4-quinolinamine                                                       151      N-[2-(1-naphthyl)ethyl]-4-                                                                           149-150° C.                                       quinolinamine                                                         152      N-[2-(2-naphthyl)ethyl]-4-                                                                           160-161° C.                                       quinolinamine                                                         153      N-[2-(2-thienyl)ethyl]-7-(trifluoro-                                                                 131-132° C.                                       methyl)-4-quinolinamine                                               154      8-fluoro-N-[2-(4-phenyl-2-thiazolyl)-                                                                134-135° C.                                       ethyl]-4-quinolinamine                                                155      8-chloro-N-[2-(1-naphthyl)ethyl]-                                                                    205-206° C.                                       4-quinolinamine                                                       156      8-chloro-N-[2-(2-naphthyl)ethyl]-                                                                    206-208° C.                                       4-quinolinamine                                                       157      α-[[(8-fluoro-4-quinolinyl)amino]-                                                             182-185° C.                                       methyl]-2-naphthalenemethanol                                         158      8-fluoro-N-[2-(1-naphthyl)ethyl]-                                                                    152-153° C.                                       4-quinolinamine                                                       159      8-fluoro-N-[2-(2-naphthyl)ethyl]-                                                                    173-174° C.                                       4-quinolinamine                                                       160      N-[2-(1-cyclohexenyl)ethyl]-N-(5,8-                                                                  oil                                                      dimethyl-4-quinolinyl)acetamide                                       161      N-(2-cyclohexylethyl)-N-(8-fluoro-                                                                   oil                                                      4-quinolinyl)acetamide                                                162      8-fluoro-N-[2-(5-methyl-2-thienyl)-                                                                  161-163° C.                                       ethyl]-4-quinolinamine                                                163      N-[2-(5-chloro-2-thienyl)ethyl]-8-                                                                   167-168° C.                                       fluoro-4-quinolinamine                                                164      8-fluoro-N-[2-(1H-imidazol-4-yl)-                                                                    230° C.                                           ethyl]-4-quinolinamine                                                165      7-chloro-N-[2-(1-cyclohexenyl)-                                                                      161-163° C.                                       ethyl]-4-quinolinamine                                                166      7-chloro-N-[2-(2-naphthyl)-                                                                          156-158° C.                                       ethyl]-4-quinolinamine                                                167      N-[2-(1-cyclohexenyl)ethyl]-7-                                                                       158-160° C.                                       (trifluoromethyl)-4-quinolinamine                                     168      N-[2-(1-cyclohexenyl)ethyl]-6-                                                                       129-131° C.                                       fluoro-4-quinolinamine                                                169      N-[2-(2-naphthyl)ethyl]-7-(tri-                                                                      127-130° C.                                       fluoromethyl)-4-quinolinamine                                         170      8-fluoro-N-[1-methyl-2-(2-thienyl)-                                                                  217-219° C.                                       ethyl]-4-quinolinamine                                                171      N-[1-methyl-2-(2-thienyl)ethyl]-                                                                     167-168° C.                                       4-quinolinamine                                                       172      8-chloro-N-[2-(2-thienyl)ethyl]-4-                                                                   161-162° C.                                       quinolinamine                                                         173      8-fluoro-N-[2-(2-thienyl)ethyl]-4-                                                                   157-158° C.                                       quinolinamine                                                         174      N-[2-(2,3-dihydro-1,4-benzodioxin-                                                                   170-171° C.                                       2-yl)ethyl]-8-fluoro-4-quinolinamine                                  175      8-fluoro-N-[2-(3-thienyl)ethyl]-4-                                                                   163-164° C.                                       quinolinamine                                                         176      8-fluoro-N-[2-(H-inldol-3-yl)ethyl]-                                                                 205-206° C.                                       4-quinolinamine                                                       177      N-(2-cyclohexylethyl)-8-fluoro-4-                                                                    145-147° C.                                       quinolinamine                                                         178      N-(2-cyclohexylethyl)-6,8-dimethyl-                                                                  155-157° C.                                       4-quinolinamine                                                       179      N-[2-(1-cyclohexenyl)ethyl]-N-(6,8-                                                                  oil                                                      dimethyl-4-quinolinyl)acetamide                                       180      8-fluoro-N-[2-(2-pyridinyl)ethyl]-                                                                   143-144° C.                                       4-quinolinamine                                                       ______________________________________                                    

                  TABLE 5                                                          ______________________________________                                         Bis[2-phenylethyl]quinolinediamines                                            EX-                                                                            AMPLE                                                                          NUMBER  COMPOUND               M.P.                                            ______________________________________                                         181     N,N'-bis(2-phenylethyl)-2,4-                                                                          70-71° C.                                        quinolinediamine                                                       182     N,N'-(2,4-quinolinediyl)bis[N-[2-(4-                                                                  oil                                                     chlorophenyl)ethyl]acetamide]                                          183     8-fluoro-N,N'-bis(2-phenylethyl)-2,4-                                                                 oil                                                     quinolinediamine                                                       184     N,N'-bis(2-phenylpropyl)-2,4-quinoline-                                                               oil                                                     diamine                                                                185     N,N'-bis[2-(4-chlorophenyl)ethyl]-                                                                    135-137° C.                                      4,6-quinolinediamine                                                   186     N,N'-bis[2-(4-chlorophenyl)ethyl]-4,7-                                                                55-60° C.                                        quinolinediamine                                                       187     N,N'-bis[2-(4-methoxyphenyl)ethyl]-                                                                   140-150° C.                                      4,7-quinolinediamine                                                   188     N,N'-bis[2-(4-chlorophenyl)ethyl]-8-                                                                  oil                                                     fluoro-2,4-quinolinediamine                                            189     N,N'-bis(2-phenylethyl)-4,8-quinoline-                                                                83-84° C.                                        diamine                                                                190     N,N'-bis[2-(2,4-dichlorophenyl)ethyl]-                                                                116-117° C.                                      8-fluoro-2,4-quinolinediamine                                          191     N,N'-(4,7-quinolinediyl)bis[N-[2-(4-                                                                  oil                                                     chlorophenyl)ethyl]acetamide]                                          ______________________________________                                    

                  TABLE 6                                                          ______________________________________                                         Bis[2-arylethyl]quinolinediamines                                              EXAMPLE                                                                        NUMBER   COMPOUND              M.P.                                            ______________________________________                                         192      N,N'-bis[2-(1-cyclohexen-yl)ethyl]-                                                                  129-131° C.                                       4,6-quinolinediamine                                                  ______________________________________                                    

                  TABLE 7                                                          ______________________________________                                         4-(2-phenylethoxy)quinolines                                                   EXAMPLE                                                                        NUMBER   COMPOUND              M.P.                                            ______________________________________                                         193      2-chloro-8-fluoro-4-[2-(4-methyl-                                                                    76-77° C.                                         phenyl)ethoxy]quinoline                                               194      5,7-dichloro-4-[2-(1,1'-biphenyl)-                                                                   100-102° C.                                       4-ylethoxy]quinoline                                                  195      4-[2-(3-methoxyphenyl)ethoxy]-8-                                                                      90-91° C.                                        fluoroquinoline                                                       196      8-fluoro-4-[2-(4-methoxyphenyl)-                                                                      70-71° C.                                        ethoxy]quinoline                                                      197      8-fluoro-4-[2-(3-phenoxyphenyl)-                                                                      73-75° C.                                        ethoxy]quinoline                                                      198      8-bromo-4-[2-(4- .sub.- t-butyl)phenyl)-                                                             115-118° C.                                       ethoxy]quinoline                                                      199      4-[2-(3,4-dimethoxyphenyl)ethoxy]-8-                                                                 113-114° C.                                       fluoroquinoline                                                       200      8-fluoro-N-[2-(1,1'-biphenyl)-4-yl-                                                                  141-142° C.                                       ethoxy]quinoline                                                      201      4-[2-(3-chlorophenyl)ethoxy]-8-fluoro-                                                                76-77° C.                                        quinoline                                                             202      7-chloro-4-(2-phenylethoxy)quinoline                                                                 oil                                             203      8-fluoro-4-[2-(3-(trifluoromethyl)-                                                                   98-99° C.                                        phenyl)ethoxy]quinoline                                               204      7-chloro-4-[2-(4-methylphenyl)ethoxy]-                                                                87-88° C.                                        quinoline                                                             205      8-fluoro-4-[2-(2-methylphenyl)ethoxy]-                                                                72° C.                                           quinoline                                                             206      8-fluoro-4-[2-(2-(trifluoromethyl)-                                                                   60° C.                                           phenyl)ethoxy]quinoline                                               207      8-chloro-4-(2-phenylethoxy)quinoline                                                                  73-74° C.                               208      4-(2-phenylethoxy)quinoline                                                                          oil                                             209      4-[2-(4-chlorophenyl)ethoxy]-8-fluoro-                                                               138-140° C.                                       quinoline                                                             210      4-[2-(4-methylphenyl)ethoxy]quinoline                                                                 59-60° C.                               211      4-[2-(4-chlorophenyl)ethoxy]quinoline                                                                106-107°  C.                             212      8-fluoro-4-[2-(4-methylphenyl)ethoxy]-                                                                89-90° C.                                        quinoline                                                             213      4-(1-methyl-2-phenylethoxy)quinoline                                                                 oil                                             214      8-fluoro-4-[1-(phenylmethyl)ethoxy]-                                                                 oil                                                      quinoline                                                             215      8-bromo-4-[2-(4-chlorophenyl)ethoxy]-                                                                112-114° C.                                       quinoline                                                             216      8-chloro-4-[2-(2-chlorophenyl)ethoxy]-                                                                90-92° C.                                        quinoline                                                             217      8-fluoro-4-[2-(2-(1-methylethyl)-                                                                    oil                                                      phenyl)-ethoxy]quinoline                                              218      8-fluoro-4-[2-(3-(phenylthio)phenyl)-                                                                oil                                                      ethoxy]quinoline                                                      219      8-fluoro-4-(2-phenylethoxy)quinoline                                                                  63-65° C.                               220      4-(2-phenylpropoxy)-8-fluoroquinoline                                                                oil                                             221      4-[2-[4-( .sub.- t-butyl)phenyl]ethoxy]-                                                              81-82° C.                                        8-fluoroquinoline                                                     222      8-fluoro-4-[2-(4-fluorophenyl)-                                                                      126-127° C.                                       ethoxy]quinoline                                                      223      4-[2-(4-bromophenyl)ethoxy]-8-                                                                       130° C.                                           fluoroquinoline                                                       224      8-fluoro-4-[2-(3-methylphenyl)ethoxy]-                                                                92° C.                                           quinoline                                                             225      8-fluoro-4-[2-(2-fluorophenyl)ethoxy]-                                                                75° C.                                           quinoline                                                             226      7-chloro-4-[2-(4-chlorophenyl)ethoxy]-                                                                96-97° C.                                        quinoline                                                             227      8-fluoro-4-[2-(2,4,6-trimethylphenyl)-                                         ethoxy]quinoline                                                      228      8-fluoro-4-[2-(2-methoxyphenyl)-                                                                      74-75° C.                                        ethoxy]quinoline                                                      229      4-[2-(2-methoxyphenyl)ethoxy]-                                                                       oil                                                      quinoline                                                             230      7-chloro-4-[2-(1,1'-biphenyl)-4-yl-                                                                   95-96° C.                                        ethoxy]quinoline                                                      231      7-chloro-4-[2-(4-( .sub.- t-butyl)phenyl)-                                                           123-124° C.                                       ethoxy]quinoline                                                      232      4-[2-(4-( .sub.- t-butyl)phenyl)ethoxy]-7-                                                             98-99° C.                                       fluoroquinoline                                                       233      4-[2-(1,1'-biphenyl)-4-ylethoxy]-7-                                                                   73-75° C.                                        fluoroquinoline                                                       234      4-[2-(4-chlorophenyl)ethoxy]-7-fluoro-                                                                81-82° C.                                        quinoline                                                             235      7-fluoro-4-[2-(4-methylphenyl)ethoxy]-                                                                85-86° C.                                        quinoline                                                             236      7-chloro-4-[2-(4-fluorophenyl)ethoxy]-                                                                80° C.                                           quinoline                                                             237      8-fluoro-4-[2-(1,1'-biphenyl)-2-yl-                                                                   55-60° C.                                        ethoxy]quinoline                                                      238      8-fluoro-4-[2-(4-( .sub.- i-propyl)phenyl)-                                                           59-60° C.                                        ethoxy]quinoline                                                      239      4-(2-phenylethoxy)-7-(trifluoro-                                                                      55-57° C.                                        methyl)quinoline                                                      240      8-chloro-4-[2-(4-fluorophenyl)-                                                                      125-127° C.                                       ethoxy]quinoline                                                      ______________________________________                                    

                  TABLE 8                                                          ______________________________________                                         4-(3-phenylpropoxy)quinolines                                                  EXAMPLE                                                                        NUMBER   COMPOUND             M.P.                                             ______________________________________                                         241      8-fluoro-4-[3-[4-( .sub.- t-butyl)phenyl]-                                                          103-105° C.                                        propoxy]quinoline                                                     242      8-chloro-4-[3-(4-chlorophenyl)-                                                                     117-119° C.                                        propoxy]quinoline                                                     243      8-fluoro-4-[(3-phenyl-2-propenyl)-                                                                  128-130° C.                                        oxy]quinoline                                                         ______________________________________                                    

                  TABLE 9                                                          ______________________________________                                         4-(2-Arylethoxy)quinolines                                                     EXAMPLE                                                                        NUMBER   COMPOUND             M.P.                                             ______________________________________                                         244      8-fluoro-4-[2-(1-naphthyl)-                                                                         121-122° C.                                        ethoxy]quinoline                                                      245      4-[2-(2-thienyl)ethoxy]-                                                                            oil                                                       quinoline                                                             246      8-fluoro-4-[2-(2-thienyl)-                                                                          77-79° C.                                          ethoxy]quinoline                                                      247      8-fluoro-4-[2-(2-naphthyl)ethoxy]-                                                                  123-124° C.                                        quinoline                                                             248      5-chloro-4-(2-cyclohexylethoxy)-2,8-                                                                100-102° C.                                        dimethylquinoline                                                     249      6-fluoro-4-(2-cyclohexylethoxy)-2-                                                                  113-115° C.                                        methylquinoline                                                       ______________________________________                                    

                  TABLE 10                                                         ______________________________________                                         Bis(2-phenylethoxy)quinolines                                                  EXAMPLE                                                                        NUMBER   COMPOUND             M.P.                                             ______________________________________                                         250      8-fluoro-2,4-bis[2-(4-methyl-                                                                       125-126° C.                                        phenyl)ethoxy]quinoline                                               251      4,8-bis[2-(4-methylphenyl)ethoxy]-                                                                  142-143° C.                                        quinoline                                                             ______________________________________                                    

                  TABLE 11                                                         ______________________________________                                         4-(3-Arylpropyl)quinolines                                                     EXAMPLE                                                                        NUMBER   COMPOUND              M.P.                                            ______________________________________                                         252      4-(3-phenylpropyl)quinoline                                           253      8-fluoro-4-(3-phenylpropyl)quinoline                                                                 43-45° C.                                254      4-(3-phenylpropyl)-7-(trifluoro-                                                                     oil                                                      methyl)quinoline                                                      255      8-chloro-4-(3-phenylpropyl)quinoline                                                                 70-71° C.                                256      8-fluoro-4-[3-(4-( .sub.-i-propyl)phenyl)-                                                           oil                                                      propyl]quinoline                                                      257      4-[3-(1,1'-biphenyl)-4-ylpropyl]-8-                                                                  oil                                                      fluoroquinoline                                                       258      8-fluoro-4-[3-(4-methylphenyl)propyl]-                                                               oil                                                      quinoline                                                             259      8-fluoro-4-[3-[3-(trifluoromethyl)-                                                                  65-66° C.                                         phenyl]propyl]quinoline                                               260      4-[3-[4-( .sub.-t-butyl)phenyl]propyl]-8-                                                            oil                                                      fluoroquinoline                                                       261      4-[3-(4-chlorophenyl)propyl]-8-fluoro-                                                               97° C.                                            quinoline                                                             ______________________________________                                    

                  TABLE 12                                                         ______________________________________                                         Additional Compounds                                                           EXAMPLE                                                                        NUMBER   COMPOUND              M.P.                                            ______________________________________                                         262      4-[2-[4-( .sub.- t-butyl)phenyl]ethoxy]-                                                              67-69° C.                                        quinoline                                                             263      8-fluoro-4-[2-(1,1'-biphenyl)-4-yl-                                                                   97-99° C.                                        ethoxy]quinoline                                                      264      8-fluoro-4-[(2-phenylethyl)sulfinyl]-                                                                NA                                                       quinoline                                                             265      8-fluoro-4-[2-[4-(2-hydroxyethyl)-                                                                   NA                                                       phenyl]ethoxy]quinoline                                               266      8-fluoro-4-[3-methoxybutoxy]-                                                                        oil                                                      quinoline                                                             267      8-fluoro-4-(4-pentenoxy)quinoline                                                                     75-78° C.                               268      8-fluoro-N-(4-phenylbutyl)-4-                                                                        104-106° C.                                       quinolinamine                                                         269      4-[2-(2-chlorophenyl)ethoxy]-8-                                                                       78-80° C.                                        fluoroquinoline                                                       270      4-[2-[1,1'-biphenyl]-4-ylbutoxy]-8-                                                                  oil                                                      fluoroquinoline                                                       271      N-[3-[4-( .sub.- t-butyl)phenyl]propyl]-8-                                                           oil                                                      fluoro-4-quinolinamine                                                272      8-fluoro-4-(4-phenoxybutoxy)quinoline                                                                 87-89° C.                               273      N-[2-(4-acetoxyphenyl)ethyl]-N-(8-                                                                   oil                                                      fluoro-4-quinolinyl)acetamide                                         274      8-fluoro-4-(3,5,5-trimethylhexyloxy)-                                                                oil                                                      quinoline                                                             275      8-fluoro-4-[2-(2,4-difluorophenyl)-                                                                   98-100° C.                                       ethoxy]quinoline                                                      276      7-chloro-4-[2-(2,4-difluorophenyl)-                                                                  103-105° C.                                       ethoxy]quinoline                                                      277      5,7-dichloro-4-[2-(4-ethoxyphenyl)-                                                                  104-105° C.                                       ethoxy]quinoline                                                      278      4-[2-(4-butoxyphenyl)ethoxy]-8-                                                                       80-82° C.                                        fluoroquinoline                                                       279      6-ethoxy-2-methyl-4-[3-(phenyl-                                                                       38-40° C.                                        methoxy)propoxy]quinoline                                             280      8-chloro-N-[2-(3-phenoxyphenyl)-                                                                     145-147° C.                                       ethyl]-4-quinolinamine                                                281      8-chloro-N-(4-phenylbutyl)-4-quino-                                                                  134-136° C.                                       linamine                                                              282      8-fluoro-4-[3-(4-phenoxyphenyl)pro-                                                                   94-96° C.                                        poxy]quinoline                                                        283      7-chloro-N-[2-(4-chlorophenyl)-                                                                      145-147° C.                                       propyl]-4-quinolinamine                                               284      4-[(4,5-dibromopentyl)oxy]-8-fluoro-                                                                  70-73° C.                                        quinoline                                                             285      8-fluoro-4-[(8-phenoxyoctyl)oxy]-                                                                     80-81° C.                                        quinoline                                                             286      6-chloro-2-methyl-4-[2-[4-( .sub.- t-butyl)-                                                          83-86° C.                                        phenyl]ethoxy]quinoline                                               287      8-fluoro-4-[(6-phenoxyhexyl)oxy]-                                                                    NA                                                       quinoline                                                             288      8-chloro-N-(2-methyl-2-                                                                              137-139° C.                                       phenylpropyl)-4-quinolinamine                                         289      8-fluoro-N-(2-methyl-2-phenylpropyl)-                                                                136-138° C.                                       4-quinolinamine                                                       290      6-methoxy-2-methyl-N-[2-(3-phenoxy-                                                                  NA                                                       phenyl)ethyl]-4-quinolinamine                                         291      8-fluoro-N-[2-[4-(phenylmethoxy)-                                                                    157-159° C.                                       phenyl]ethyl]-4-quinolinamine                                         292      7-fluoro-4-[2-(4-bromophenoxy)-                                                                      127-129° C.                                       ethoxy]quinoline                                                      293      N-[2-(4-hydroxyphenyl)ethyl]-8-                                                                      249-251° C.                                       fluoro-4-quinoline                                                    294      8-fluoro-4-[3-[3-(trifluoromethyl)-                                                                   67-69° C.                                        phenyl]propoxy]quinoline                                              295      8-fluoro-4-(2-phenylcyclohexyloxy)-                                                                  NA                                                       quinoline                                                             296      8-chloro-N-[2-(2,4-difluorophenyl)-                                                                  206-208° C.                                       ethyl]-4-quinolinamine                                                297      8-fluoro-4-[2-[4-(1,1,2,2-tetra-                                                                      70-72° C.                                        fluoroethoxy)phenyl]ethoxy]quinoline                                  298      N-[2-[3,4-bis(phenylmethoxy)-                                                                        137-139° C.                                       phenyl]ethyl]-8-fluoro-4-quinolinamine                                299      4-[2-(6-chloro-1,3-benzodioxol-5-yl)-                                                                143-145° C.                                       ethoxy]-8-fluoroquinoline                                             300      8-fluoro-N-[2-(4-ethoxyphenyl)ethyl]-                                                                179-181° C.                                       4-quinolinamine                                                       301      N-[2-(4-ethoxyphenyl)ethyl]-4-                                                                       125-126° C.                                       quinolinamine                                                         302      8-fluoro-4-[3-(4-ethoxyphenyl)propyl]-                                                               oil                                                      quinoline                                                             303      4-[3-(4-ethoxyphenyl)propyl]quinoline                                                                oil                                             304      8-fluoro-4-[3-(4-methoxyphenyl)-                                                                     oil                                                      propyl]quinoline                                                      305      8-fluoro-4-(2,2-dimethylbutoxy)-                                                                     oil                                                      quinoline                                                             306      8-fluoro-N-[2-[4-(butoxy)phenyl]-                                                                    118-120° C.                                       ethyl]-4-quinolinamine                                                307      7-[(8-fluoro-4-quinolinyl)oxy]-                                                                       94-96° C.                                        heptanenitrile                                                        308      8-fluoro-4-[2-(3,4-difluorophenyl)-                                                                   87-89° C.                                        ethoxy]quinoline                                                      309      8-fluoro-4-[2-(1,3-benzodioxol-5-                                                                    103-105° C.                                       yl)ethoxy]quinoline                                                   310      4-[2-(2,6-dichlorophenyl)ethoxy]-                                                                    128-129° C.                                       8-fluoroquinoline                                                     311      8-chloro-4-[2-(2-chloro-4-fluoro-                                                                    104-106° C.                                       phenyl)ethoxy]quinoline                                               312      8-fluoro-N-[2-(3-methoxyphenyl)-                                                                     153-155° C.                                       ethyl]-4-quinolinamine                                                313      8-fluoro-N-[2-(4-ethylphenyl)-                                                                       162-164° C.                                       ethyl]-4-quinolinamine                                                314      8-fluoro-4-[2-[4-(heptyloxy)phenyl]-                                                                  45-47° C.                                        ethoxy]quinoline                                                      315      (E)-8-fluoro-4-[(2-phenylethenyl)-                                                                    99-101° C.                                       oxy]quinoline                                                         316      (Z)-8-fluoro-4-[(2-phenylethenyl)-                                                                    95-97° C.                                        oxy]quinoline                                                         317      8-fluoro-N-[2-[4-(propoxy)phenyl]-                                                                   140-142° C.                                       ethyl]-4-quinolinamine                                                318      8-chloro-4-[2-(3,4-difluorophenyl)-                                                                   84-86° C.                                        ethoxy]quinoline                                                      319      4-[3-[4-( .sub.- i-propyl)phenyl]propyl]-                                                            oil                                                      quinoline                                                             320      7-chloro-4-[2-(1,3-benzodioxol-5-yl)-                                                                 75-77° C.                                        ethoxy]quinoline                                                      321      8-fluoro-4-[2-(4-methoxyphenoxy)-                                                                    107-109° C.                                       ethoxy]quinoline                                                      322      8-fluoro-4-[2-[4-(3-methylphenoxy)-                                                                   98-100° C.                                       phenyl]ethoxy]quinoline                                               323      8-chloro-4-[2-(2,4-difluorophenyl)-                                                                  118-120° C.                                       ethoxy]quinoline                                                      324      N-[2-(5-bromo-2-methoxyphenyl)-                                                                      176-178° C.                                       ethyl]-8-fluoro-4-quinolinamine                                       325      8-fluoro-4-[2-(4-propoxyphenyl)-                                                                     108-110° C.                                       ethoxy]quinoline                                                      326      8-fluoro-4-(2-phenoxyethoxy)quinoline                                                                118-120° C.                              327      8-fluoro-N-[4-[4-(trifluoromethyl)-                                                                  110-112° C.                                       phenyl]butyl]-4-quinolinamine                                         328      8-fluoro-N-[2-[4-(1,1,2,2-tetra-                                                                     168-170° C.                                       fluoroethoxy)phenyl]ethyl]-4-quinolin-                                         amine                                                                 ______________________________________                                    

The procedures described in the following detailed Examples are representative of the procedures used to prepare the compounds of the other Examples.

EXAMPLE 4N-Ethyl-N-(2-phenylethyl)-4-quinolinamine

To a suspension of 0.59 g of lithium aluminum hydride in 100 mL of dry ether was added, dropwise, a solution of 2.3 g of N-(2-phenylethyl)-N-(4-quinolinyl)acetamide dissolved in 50 mL of dry ether. The mixture was heated to reflux for seven hours. Excess lithium aluminum hydride was then destroyed by adding 100 mL of water to the mixture. The solvent was then removed, and the residue was dissolved in chloroform. After washing with water, the mixture was then dried and concentrated. Using HPLC (silica gel, CH₂ Cl₂ →EtOAc), 0.80 g of the title product was isolated. Yield 36.7%. M.P. oil.

EXAMPLE 10 N-[2-(4-Chlorophenyl)ethyl-N-[8-fluoro-4-quinolinyl]acetamide

A mixture of 2.0 g of N-[2-(4-chlorophenyl)ethyl]-8-fluoro-4-quinolinamine and 5.0 mL of acetic anhydride was refluxed overnight. The mixture was then cooled, and solvents were removed by reducing pressure. The residue was washed with water and then dried. The resulting oil was passed over a silica gel column with ethyl acetate, and the front running spot was collected, producing 0.8 g of the title product as a thick oil.

EXAMPLE 25 2-Chloro-N-(2-phenylethyl)-4-quinolinamine

To 0.6 g of 2-hydroxy-N-(2-phenylethyl)-4-quinolinamine was added 15 mL of POCl₃. The mixture was heated to reflux overnight, then cooled and concentrated to dryness. A mixture of ammonium hydroxide in water was added, then the product was extracted into CH₂ Cl₂. This solution was concentrated to dryness, and the product was recrystallized from pentane/CH₂ Cl₂, giving 0.55 g of the title product. Yield 85.9%. M.P. 132°-133° C.

EXAMPLE 69 3-Chloro-N-(2-chloro-2-phenylethyl)-4-quinolinamine

A mixture of 4.1 g of 1-phenyl-2-(4-quinolinylamine)ethanol, 100 mL of POCl₃ and 6.5 g of PCl₅ was heated to reflux for 18 hours, then cooled and concentrated to dryness. An ice/water mixture was added, then the product was extracted into CH₂ Cl₂. This solution was concentrated to dryness, and the residue was purified by HPLC (silica gel column eluted with pentane/CH₂ Cl₂ (50:50)). Fractions containing the product were combined and concentrated to dryness producing 0.433 g of the title product. Yield 8.7%. M.P. oil.

EXAMPLE 97 8-Fluoro-N-[2-(2-trifluoromethyl)phenyl]-4-quinolinamine

To 2.0 g of 4-chloro-8-fluoroquinoline was added 4.1 g of 2-[2-(trifluoromethyl)phenyl]ethylamine. The mixture was stirred and heated to 160°-165° C. under nitrogen for two hours, then cooled, and 200 mL of a 50:50 mixture of ammonium hydroxide and water was added. The product was extracted into CH₂ Cl₂, which was concentrated to dryness. Recrystallization from a pentane/CH₂ Cl₂ mixture yielded 1.5 g of the title product. Yield 41.6%.

EXAMPLE 154 8-Fluoro-N-[2-(4-phenyl-2-thiazolyl)ethyl]-4-quinolinamine

To 1.0 g of 4-chloro-8-fluoroquinoline was added 2.6 g of 2-β-aminoethyl-4-phenylthiazole monohydrochloride. The mixture was stirred under nitrogen and heated to 170°-175° C. for one hour. The mixture was then cooled and 250 mL of a 50:50 mixture of ammonium hydroxide and water was added. The product was extracted into CH₂ Cl₂, which was then concentrated to dryness. Recrystallizing from pentane/CH₂ Cl₂ gave 0.410 g of the title product. Yield 21.6%. M.P. 134°-135° C.

EXAMPLE 159 8-Fluoro-N-[2-(2-naphthyl)ethyl]-4-quinolinamine

A mixture of 2.0 g of 4-chloro-8-fluoroquinoline and 3.8 g of 2-(2-naphthyl)ethyl amine was heated under nitrogen to 160°-165° C. for one hour. Then 200 mL of a 50:50 mixture of ammonium hydroxide in water was added. The product was extracted from the mixture into CH₂ Cl₂, which was then concentrated to dryness. The residue was recrystallized from pentane/ethyl acetate to give 1.4 g of the title product. Yield 41.2%. M.P. 173°-174° C.

EXAMPLE 173 8-Fluoro-N- [2-(2-thienyl)ethyl]-4-quinolinamine

A mixture of 2.0 g of 4-chloro-8-fluoroquinoline and 2.8 g of 2-(2-thienyl)ethyl amine was heated under nitrogen to 160°-165° C. for two hours, then cooled and combined with 200 mL of a 50:50 mixture of ammonium hydroxide and water. The product was extracted into CH₂ Cl₂, which was then concentrated to dryness. The residue was recrystallized from pentane/CH₂ Cl₂ to give 1.0 g of the title product. Yield 34.5%. M.P. 157°-158° C.

EXAMPLE 181 Bis[2-phenylethyl ]-2,4-quinolinediamine

To 2.0 g of 2,4-dichloroquinoline was added 4.8 g of 2-phenylethylamine, and the mixture was heated to 150°-160° C. under nitrogen for 18 hours. The mixture was then cooled and a solution of ammonium hydroxide and water was added. The product was extracted into CH₂ Cl₂, which was then concentrated to dryness, giving an oil. To the oil, 100 mL of pentane and CH₂ Cl₂ was added and the oil went into solution. This solution was cooled, and the title product crystallized. Yield 44.4%. M.P. 70°-71° C.

EXAMPLE 186 N,N'-Bis[2-(4-chlorophenyl)ethyl]-2,7-quinolinediamine

A mixture of 2.0 g of 4-chloro-7-fluoroquinoline and 3.5 g of 2-(4-chlorophenyl)ethyl amine was heated neat until fuming began. The mixture was then cooled. The product was extracted into a CHCl₃ /ammonium hydroxide solution, which was then washed with water. Solvent was removed by reducing pressure. The residue was placed on a silica gel column with acetone, then flushed with ethanol. Solvent was removed by reducing pressure, giving the title product as a yellow-brown foam. Yield 1.1 g. M.P. 55°-60° C.

EXAMPLE 209 4-[2-(4-Chlorophenyl)ethoxy]-8-fluoroquinoline

To 1.2 g of sodium hydride in 50 mL of DMF was added 3.9 g of 2-(4-chlorophenyl)ethyl alcohol. The mixture was stirred at room temperature for one hour, then 4.5 g of 4-chloro-8-fluoroquinoline in 10 mL of DMF was added, the the mixture was heated to reflux for two hours. Then the mixture was allowed to cool to room temperature while it was stirred for four hours, after which it was poured into an ice/water mixture. The mixture was filtered, and the filter cake was washed with H₂ O. Recrystallization from pentane/ethyl acetate gave 0.840 g of the title product. Yield 11.2%. M.P. 139°-140° C.

EXAMPLE 221 4-[2- 4-(t-But yl)phenyl]ethoxy]-8-fluoroquinoline

To a mixture of 1.1 g of sodium hydride in 50 mL of DMF was added 4.0 g of 2-[4-(1,1-dimethylethyl)phenyl]ethyl alcohol, and the mixture was stirred for one hour at room temperature. Then 4.0 g of 4-chloro-8-fluoroquinoline in 20 mL of DMF were added, and the mixture was stirred at room temperature overnight. Then the mixture was poured into an ice/water mixture, and the solid was collected and recrystallized from ethyl acetate/pentane to give 2.3 g of the title product. Yield 32.4%. M.P. 81°-82° C.

EXAMPLE 238 8-Fluoro-4-[2-[4-(i-propyl)phenyl]ethoxy]quinoline

To a suspension of 0.96 g of sodium hydride in 10 mL of dry DMF was added 3.6 g of 4-chloro-8-fluoroquinoline. The mixture was cooled in an ice/water bath, and 3.3 g of 2-[4-(1-methylethyl)phenyl]ethyl alcohol was added. The mixture was stirred overnight, then diluted with ice and water. The pH was adjusted to 7, then the product was extracted into CH₂ Cl₂. The CH₂ Cl₂ layer was separated, filtered, and evaporated in vacuo. An azeotrope with xylene was formed to facilitate removal of residual DMF. The residue was chromatographically purified on a silica gel column, eluting with CH₂ Cl₂, →5% EtOAc/CH₂ Cl₂ →10% EtOAc/CH₂ Cl₂. The fractions containing product were combined and evaporated to give an oil, which crystallized on adding ether. Recrystallization yielded 2.5 g of title product. M.P. 56°-60° C.

EXAMPLES 212 AND 251 8-fluoro-4-[2-(4-methylphenyl)ethoxy]quinoline, 4,8-Bis[2-(4-methylphenyl)ethoxy]quinoline

To a solution of 1.2 g of sodium hydride in 50 ml of DMF was added 3.4 g of 2-(4-methylphenyl)ethanol, and the mixture was stirred for one hour at room temperature. Then 4.5 g of 4-chloro-8-fluoroquinoline were added, the mixture was heated to reflux for five hours, and then cooled to room temperature, and poured into a mixture of ice in water. The solid phase was collected and dried. TLC showed three products. These were separated by HPLC (silica gel, 70% pentane/30% EtOAc) giving

1.84 g of 8-fluoro-4-[2-(4-methylphenyl)ethoxy]quinoline (Yield: 26.3%; M.P. 89°-90° C.)

0.610 g of 4-chloro-8-[2-(4-methylphenyl)ethoxy]quinoline (Yield: 8.7%; M.P. 74°-75° C.); and 0.450 g of 4,8-bis[2-(4-methylphenyl)ethoxy]quinoline (Yield: 6.4%; M.P. 142°-143° C.).

EXAMPLE 261 4-[3-(4-chlorophenyl)propyl]-8-fluoroquinoline

A mixture of 3.63 g of 4-chloroquinoline and 5.3 g of 5-[2-(4-chlorophenyl)ethyl]barbituric acid was heated to 150° C. for 11/4 hours, to form 5-[2-(4-chlorophenyl)ethyl]-5-(4-quinolinyl)barbituric acid. This compound was hydrolyzed, without isolation, by adding 4 g of NaOH in 40 ml of water and refluxing for four hours. The mixture was cooled, acidified with HCl and refluxed for several hours, cooled, and neutralized with dilute NaOH. The desired product was extracted into CH₂ Cl₂, which was then filtered through phase separating paper and evaporated to dryness. The residue was absorbed onto silica gel and chromatographed over silica gel using CH₂ Cl₂. Fractions containing product were combined to give 2.69 g of crystalline material. This was recrystallized from a petroleum ether/CH₂ Cl₂ mixture to give 2.35 g of the title product. Yield: 39%. M.P. 97° C.

UTILITY Plant Pathology

The compounds of the present invention have been found to control fungi, particularly plant pathogens. When employed in the treatment of plant fungal diseases, the compounds are applied to the plants in a disease inhibiting and "phytologically acceptable amount". The term "disease inhibiting" and "phytologically acceptable amount," as used herein, refers to an amount of a compound of the invention which kills or inhibits the plant disease for which control is desired, but is not significantly toxic to the plant. This amount will generally be from about 1 to 1000 ppm, with 10 to 500 ppm being preferred. The exact concentration of compound required varies with the fungal disease to be controlled, the type formulation employed, the method of application, the particular plant species, climate conditions and the like. The compounds of the invention may also be used to protect stored grain and other non-plant loci from fungal infestation.

Greenhouse Tests

The following experiments were performed in the laboratory to determine the fungicidal efficacy of the compounds of the invention.

Test 1

This screen was used to evaluate the efficacy of the present compounds against a variety of different organisms that cause plant diseases.

The test compounds were formulated for application by dissolving 50 mg of the compound into 1.25 ml of solvent. The solvent was prepared by mixing 50 ml of "Tween 20" with 475 ml of acetone and 475 ml of ethanol. The solvent/compound solution was diluted to 125 ml with deionized water. The resulting formulation contains 400 ppm test chemical. Lower concentrations were obtained by serial dilution with the solvent-surfactant mixture.

The formulated test compounds were applied by foliar spray. The following plant pathogens and their corresponding plants were employed.

    ______________________________________                                                        Designation in                                                  Pathogen       Following Tables                                                                            Host                                               ______________________________________                                         Erysiphe graminis tritici                                                                     POWD         wheat                                              (powdery mildew)                                                                              MDEW                                                            Pyricularia oryzae                                                                            RICE         rice                                               (rice blast)   BLAS                                                            Puccinia recondita tritici                                                                    LEAF         wheat                                              (leaf rust)    RUST                                                            Botrytis cinerea                                                                              GRAY         grape berries                                      (gray mold)    MOLD                                                            Pseudoperonospora cubensis                                                                    DOWN         squash                                             (downy mildew) MDEW                                                            Cercospora beticola                                                                           LEAF         sugar beet                                         (leaf spot)    SPOT                                                            Venturia inaequalis                                                                           APPL         apple seedling                                     (apple scab)   SCAB                                                            Septoria tritici                                                                              LEAF         wheat                                              (leaf blotch)  BLOT                                                            ______________________________________                                    

The formulated technical compounds were sprayed on all foliar surfaces of the host plants (or cut berry) to past run-off. Single pots of each host plant were placed on raised, revolving pedestals in a fume hood. Test solutions were sprayed on all foliar surfaces. All treatments were allowed to dry and the plants were inoculated with the appropriate pathogens within 2-4 hours.

The effectiveness of test compounds in controlling disease was rated on the following scale:

0=not tested against specific organism

-=0-19% control at 400 ppm

+=20-89% control at 400 ppm

++=90-100% control at 400 ppm

+++=90-100% control at 100 ppm.

Table 13 gives the results.

                                      TABLE 13                                     __________________________________________________________________________     EX.                                                                               POWD RICE LEAF                                                                               GRAY DOWN LEAF                                                                               APPL                                                                               LEAF                                        NO.                                                                               MDEW BLAST                                                                               RUST                                                                               MOLD MDEW SPOT                                                                               SCAB                                                                               BLOT                                        __________________________________________________________________________      1 +    +    +   +    ++   0   -   -                                            2 -    -    -   -    +++  0   -   -                                            3 -    ++   +   -    +++  0   -   -                                            4 +    +    ++  -    ++   0   -   -                                            5 ++   ++   +++ -    +++  0   -   +++                                          6 ++   +    +   +    ++   0   -   -                                            7 +    +    +++ -    +++  -   -   +++                                          8 +    ++   +   -    +++  + ++                                                                               -   +                                            9 +    +    +   -    +++  -   -   -                                            10                                                                               ++   +++  +++ -    ++   +++ -   +++                                          11                                                                               -    ++   +++ -    ++   +++ -   -                                            12                                                                               +    ++   +++ -    ++   +++ -   ++                                           13                                                                               -    ++   ++  -    ++   -   -   -                                            14                                                                               -    +    +   -    +++  +++ -   -                                            15                                                                               -    +    +   -    +++  +++ +   -                                            16                                                                               -    +    +   -    +++  +++ -   -                                            17                                                                               ++   +    ++  -    ++   0   -   -                                            18                                                                               +    ++   ++  +    ++   0   -   -                                            19                                                                               +    ++   ++  -    +++  0   -   -                                            20                                                                               +    +    +   -    +++  0   -   -                                            21                                                                               +    +    +   -    ++   0   -   -                                            22                                                                               +    +    +   -    +++  0   -   -                                            23                                                                               +    +    +   -    +++  0   -   -                                            24                                                                               +    +    +   -    +++  0   -   -                                            25                                                                               +    +    ++  -    +++  0   -   -                                            26                                                                               +    +    -   -    +++  0   -   -                                            27                                                                               +    ++   +   -    +++  0   -   -                                            28                                                                               +    ++   +   -    +++  0   -   -                                            29                                                                               -    +    +   -    -    0   0   0                                            30                                                                               -    +    +   -    +++  0   -   -                                            31                                                                               ++   +    +   -    +++  0   -   -                                            32                                                                               +    +    -   -    +++  0   -   -                                            33                                                                               -    +    +   -    +++  0   -   -                                            34                                                                               +    +    ++  -    +++  +   -   -                                            35                                                                               +    +    +   -    +++  +++ -   -                                            36                                                                               +    +++  +++ -    +++  +++ -   +++                                          37                                                                               +    -    +   -    +    0   0   0                                            38                                                                               +    -    ++  -    +++  +   -   -                                            39                                                                               +++  +++  +++ -    +++  0   0   0                                            40                                                                               -    ++   +++ -    +    0   0   0                                            41                                                                               +    ++   +++ -    ++   +++ -   +                                            42                                                                               +++  +    ++  -    +++  +++ -   -                                            43                                                                               +    +    -   -    ++   +++ -   -                                            44                                                                               +++  +    +   -    +++  +++ +   -                                            45                                                                               +    ++   +   -    ++   +++ -   -                                            46                                                                               +    ++   +   -    ++   +++ +   +                                            47                                                                               +    -    +   -    +    0   0   0                                            48                                                                               +    +    +   -    ++   +   -   -                                            49                                                                               -    +    +   -    +    0   0   0                                            50                                                                               +++  -    ++  -    +++  -   -   -                                            51                                                                               -    +    +   -    +++  +++ -   -                                            52                                                                               -    +    +   -    +++  +   -   +++                                          53                                                                               +++  +    +   -    +++  +++ -   +                                            54                                                                               -    ++   +   -    +++  +++ -   +                                            55                                                                               +    ++   +   -    ++   +++ -   -                                            56                                                                               -    ++   ++  -    +++  +++ -   +                                            57                                                                               -    ++   +   -    ++   +++ -   -                                            58                                                                               -    -    +   -    +++  0   0   0                                            59                                                                               +    +    -   -    -    0   0   0                                            60                                                                               ++   +++  ++  -    +++  0   0   0                                            61                                                                               -    ++   ++  -    +++  0   0   0                                            62                                                                               -    ++   ++  -    +++  -   -   +                                            63                                                                               -    +    +++ -    ++   0   0   0                                            64                                                                               +    -    +   -    +++  0   0   0                                            65                                                                               +    +    ++  -    +++  -   -   +                                            66                                                                               +    ++   +++ -    +++  +++ -   +                                            67                                                                               -    +    +   -    ++   +   -   -                                            68                                                                               +    +    +++ -    ++   -   -   +++                                          69                                                                               +    +    +   -    +++  -   -   -                                            70                                                                               +++  +    +   -    -    -   -   -                                            71                                                                               +    +    +++ -    +++  +++ -   +                                            72                                                                               ++   +++  +++ -    +++  0   0   0                                            73                                                                               -    +    -   -    ++   -   -   -                                            74                                                                               +    +    +++ -    +++  +++ -   -                                            75                                                                               +    +    ++  -    +++  -   -   +                                            76                                                                               ++   +++  +++ -    +++  -   +   +++                                          77                                                                               +    +    ++  -    +++  -   +   -                                            78                                                                               +    ++   +++ -    +++  +++ -   +                                            79                                                                               +    ++   ++  -    +++  +++ -   +                                            80                                                                               +    ++   ++  -    +++  +   -   -                                            81                                                                               +    ++   ++  -    +++  +   -   -                                            82                                                                               +    +++  +++ -    +++  +   -   +++                                          83                                                                               +    ++   +++ +++  ++   +   -   -                                            84                                                                               +++  ++   ++  -    ++   +   -   -                                            85                                                                               -    -    +   -    -    0   0   0                                            86                                                                               -    -    +   -    +    0   0   0                                            87                                                                               -    -    +   -    +++  -   -   -                                            88                                                                               -    -    ++  -    ++   +   -   -                                            89                                                                               -    -    +   -    +++  0   0   0                                            90                                                                               -    +++  +++ -    +++  0   0   0                                            91                                                                               +    +    -   -    ++   -   -   -                                            92                                                                               +    ++   +++ -    ++   +   -   +++                                          93                                                                               -    -    -   -    -    +   -   +                                            94                                                                               +    +++  +++ -    ++ + +++ -   +                                            95                                                                               +    ++   +++ +    +++  +   +   +++                                          96                                                                               +    +++  +++ -    +++  +++ -   +++                                          97                                                                               +    +++  +++ -    +++  +++ -   +++                                          98                                                                               -    +    ++  -    ++   -   -   -                                            99                                                                               -    ++   +++ -    +++  +   -   -                                           100                                                                               +    +    +   -    +    0   0   0                                           101                                                                               +++  -    +   -    +++  +++ +   -                                           102                                                                               +    +    -   -    -    0   0   0                                           103                                                                               +    ++   ++  -    +++  +   +++ +                                           104                                                                               -    -    -   -    ++   +   +   -                                           105                                                                               +++  ++   +++ -    +++  +   -   +                                           106                                                                               ++   +    +   -    +    +   -   +                                           107                                                                               ++   +    +   -    +++  -   -   -                                           108                                                                               +    +    ++  -    +    -   -   +++                                         109                                                                               +    +    ++  -    +++  0   0   0                                           110                                                                               -    +    ++  -    ++   0   0   0                                           111                                                                               +    ++   +++ -    +++  -   -   +++                                         112                                                                               -    -    +   -    +++  -   -   -                                           113                                                                               +    +++  +++ -    +++  -   -   +++                                         114                                                                               +++  +++  +++ -    +++  +++ -   +++                                         115                                                                               -    +    -   -    +    0   0   0                                           116                                                                               -    +    +++ -    +++  +   +   -                                           117                                                                               +    +    +   -    +++  +   -   -                                           118                                                                               -    +    -   -    -    -   -   -                                           119                                                                               +    +    +   -    ++   -   +   +                                           120                                                                               -    +    +   -    ++   +++ -   -                                           121                                                                               +    -    ++  -    +    0   0   0                                           122                                                                               -    ++   +   -    ++   -   -   -                                           123                                                                               -    +    +   -    +++  -   -   -                                           124                                                                               +++  +    +   -    -    -   -   -                                           125                                                                               +    -    -   -    -    0   0   0                                           126                                                                               ++   +++  +   -    +    -   -   +                                           127                                                                               +    +    +   -    +    0   0   0                                           128                                                                               -    +    +   -    -    0   0   0                                           129                                                                               -    +    ++  -    +    -   +   -                                           130                                                                               -    -    -   -    -    0   0   0                                           131                                                                               -    -    -   -    +    0   0   0                                           132                                                                               -    -    -   -    -    0   0   0                                           133                                                                               -    +    +   -    +    0   0   0                                           134                                                                               +    ++   +   -    +++  0   0   0                                           135                                                                               -    -    -   -    +++  -   -   +                                           136                                                                               +    -    -   -    +++  -   -   -                                           137                                                                               +    +++  +   -    +++  0   0   0                                           138                                                                               -    +    +   -    +++  0   0   0                                           139                                                                               +    +    +   -    ++   -   -   -                                           140                                                                               +    +++  +++ -    +++  +++ +   +++                                         141                                                                               -    ++   +   -    +    0   0   0                                           142                                                                               -    ++   ++  -    +++  0   0   0                                           143                                                                               ++   ++   +++ -    +++  +   -   +                                           144                                                                               -    +    ++  -    +++  +   +   -                                           145                                                                               -    +    +   -    +++  +   -   -                                           146                                                                               -    -    -   -    +    0   0   0                                           147                                                                               -    +    +   -    +++  -   -   -                                           148                                                                               -    +    +   -    ++   +   -   -                                           149                                                                               +    +    ++  -    ++   +++ -   +                                           150                                                                               +    +    ++  -    ++   +++ -   +++                                         151                                                                               +    +    ++  -    +++  +   -   +                                           152                                                                               ++   +++  ++  -    +++  +++ -   +++                                         153                                                                               +    ++   ++  -    +    -   -   -                                           154                                                                               ++   +    +++ -    +++  +   +   +                                           155                                                                               -    +    -   -    +++  -   -   -                                           156                                                                               -    +    +   -    +++  -   -   -                                           157                                                                               -    ++   ++  -    +++  0   0   0                                           158                                                                               +    +++  +++ -    +++  +   -   +++                                         159                                                                               ++   +++  +++ -    +++  +   -   +++                                         160                                                                               -    +    -   -    -    0   0   0                                           161                                                                               +    +    -   -    +    0   0   0                                           162                                                                               +    +    ++  -    +++  -   -   -                                           163                                                                               ++   +    +++ -    ++   +++ -   -                                           164                                                                               -    +    +   +    ++   +   -   -                                           165                                                                               +    ++   ++  -    +++  +++ +   -                                           166                                                                               +    +    +   -    +++  -   -   +                                           167                                                                               +    -    -   -    +    0   0   0                                           168                                                                               +    ++   ++  -    +++  -   -   -                                           169                                                                               +    ++   +   -    ++   -   -   -                                           170                                                                               +    +    ++  -    +    -   -   -                                           171                                                                               -    +    +   -    +    +   -   +                                           172                                                                               +    +    +   -    +    -   -   -                                           173                                                                               +    +    ++  -    +++  +++ -   +                                           174                                                                               +    +    ++  -    +++  -   -   +                                           175                                                                               +    +    +++ -    +++  -   -   +                                           176                                                                               +    +    +   -    ++   +   -   -                                           177                                                                               ++   +++  +++ -    +++  0   0   0                                           178                                                                               -    +    ++  -    +++  0   0   0                                           179                                                                               -    -    -   -    ++   +   +   -                                           180                                                                               ++   +    -   -    ++   +   -   +                                           181                                                                               +    +    +   -    +++  0   -   -                                           182                                                                               -    +    -   -    -    0   0   0                                           183                                                                               -    ++   ++  -    +++  +   +   -                                           184                                                                               -    +    ++  -    ++   -   -   -                                           185                                                                               -    +    +   -    +    0   0   0                                           186                                                                               -    -    +   -    +++  +   -   +                                           187                                                                               -    +    +   -    +++  -   -   -                                           188                                                                               -    ++   +   -    ++   0   0   0                                           189                                                                               -    +    +   -    +    -   -   -                                           190                                                                               -    +    +++ -    -    -   -   -                                           191                                                                               -    +    ++  -    -    0   0   0                                           192                                                                               -    -    ++  -    +++  -   -   +                                           193                                                                               -    -    +   -    -    0   0   0                                           194                                                                               +    -    -   -    -    0   0   0                                           195                                                                               +++  +++  +++ -    +++  0   0   0                                           196                                                                               +++  +++  +++ -    +++  0   0   0                                           197                                                                               +++  +++  +++ -    +    0   0   0                                           198                                                                               -    -    -   -    -    0   0   0                                           199                                                                               ++   ++   +++ -    +++  0   0   0                                           200                                                                               +++  +++  +++ -    +    +   +   +++                                         201                                                                               +++  +    +++ -    +++  +++ +   +++                                         202                                                                               +++  +    ++  -    ++   +   -   +                                           203                                                                               +    +++  +++ -    ++   +   +   ++                                          204                                                                               +    -    +   -    +    0   0   0                                           205                                                                               ++   +++  +++ -    +++  0   0   0                                           206                                                                               +++  +++  +++ -    +++  0   0   0                                           207                                                                               ++   +++  +++ -    +++  +   +   +++                                         208                                                                               ++   +++  +++ -    +++  +   -   +                                           209                                                                               +++  +++  +++ -    +++  +++ +   +++                                         210                                                                               ++   +++  +++ -    +++  +   -   +++                                         211                                                                               ++   +++  +++ -    +++  +++ -   +++                                         212                                                                               ++   +++  +++ -    +++  -   +++ +++                                         213                                                                               +    ++   ++  -    +++  -   +   +                                           214                                                                               +    +++  +   -    ++   0   0   0                                           215                                                                               -    +    +   -    ++   0   0   0                                           216                                                                               ++   ++   ++  -    ++   0   0   0                                           217                                                                               +++  +++  ++ +                                                                               -    +++  0   0   0                                           218                                                                               +++  +++  +++ -    +++  0   0   0                                           219                                                                               ++   +++  +++ -    +++  +   +   +                                           220                                                                               ++   +    ++  -    ++   -   +   -                                           221                                                                               +    -    +++ -    +++  +++ +   +++                                         222                                                                               +    +    +++ -    +++  +   +++ +++                                         223                                                                               ++   +++  +++ -    -    0   0   0                                           224                                                                               ++   +++  +++ -    +++  0   0   0                                           225                                                                               ++   +++  +++ -    +++  0   0   0                                           226                                                                               +    -    +   -    +    0   0   0                                           227                                                                               -    +    +   -    -    0   0   0                                           228                                                                               ++   +++  +++ -    +++  +   +++ +++                                         229                                                                               +    +++  ++  -    +++  -   -   +                                           230                                                                               ++   -    +   -    -    -   -   -                                           231                                                                               +    -    -   -    -    0   0   0                                           232                                                                               -    -    -   -    -    0   0   0                                           233                                                                               +    ++   ++  -    +    -   -   +                                           234                                                                               +    +    ++  -    +    +   -   +                                           235                                                                               +    ++   ++  -    +    -   -   +                                           236                                                                               +++  -    +   -    -    -   -   -                                           237                                                                               ++   ++   +   -    -    0   0   0                                           238                                                                               +++  +++  +++ +    ++   0   0   0                                           239                                                                               +++  ++   ++  -    ++   0   0   0                                           240                                                                               -    +    ++  -    -    0   0   0                                           241                                                                               -    -    -   -    -    0   0   0                                           242                                                                               -    -    -   -    -    0   0   0                                           243                                                                               -    -    -   -    -    0   0   0                                           244                                                                               +    ++   +   -    +    -   -   +                                           245                                                                               +    ++   ++  -    ++   -   -   -                                           246                                                                               ++   +++  +++ -    +++  +   +++ +++                                         247                                                                               ++   +++  +++ -    +    -   -   +++                                         248                                                                               +    -    -   -    -    0   0   0                                           249                                                                               -    -    -   -    -    0   0   0                                           250                                                                               -    -    +   -    +    0   0   0                                           251                                                                               -    +    -   -    +    -   -   -                                           252                                                                               ++   ++   +++ -    ++   -   +   +                                           253                                                                               +++  ++   +++ -    ++   +   +++ +                                           254                                                                               ++   ++   -   -    -    0   0   0                                           255                                                                               +    +++  +++ -    +    0   0   0                                           256                                                                               +++  +++  +++ -    ++   0   0   0                                           257                                                                               +++  +    +++ -    +++  0   0   0                                           258                                                                               ++   +++  ++  -    ++   +   -   +                                           259                                                                               +    +++  +++ +    +++  -   +++ +++                                         260                                                                               ++   +++  +++ -    +++  +   -   +++                                         261                                                                               +    +    +++ -    +    -   +   +                                           262                                                                               -    ++   +++ -    +++  0   0   0                                           263                                                                               +    +    +   -    -    0   0   0                                           264                                                                               -    -    +   -    0    0   0   0                                           265                                                                               -    ++   ++  -    -    0   0   0                                           266                                                                               -    -    -   -    -    0   0   0                                           267                                                                               ++   +++  ++  -    +    0   0   0                                           268                                                                               +    +++  +++ -    +++  0   0   0                                           269                                                                               ++   +++  +++ -    +++  0   0   0                                           270                                                                               -    +    -   -    -    0   0   0                                           271                                                                               -    +++  +   -    +++  0   0   0                                           272                                                                               -    +    -   -    +    0   0   0                                           273                                                                               +    ++   +   -    +    0   0   0                                           274                                                                               ++   ++   ++  -    +    0   0   0                                           275                                                                               +++  +++  +++ -    +++  0   0   0                                           276                                                                               +++  -    +   -    -    0   0   0                                           277                                                                               ++   -    -   -    -    0   0   0                                           278                                                                               +++  +++  +++ -    +++  0   0   0                                           279                                                                               -    ++   ++  -    ++   0   0   0                                           280                                                                               +++  +++  +++ -    +++  0   0   0                                           281                                                                               +    +++  +   -    +++  0   0   0                                           282                                                                               -    +    -   -    -    0   0   0                                           283                                                                               +    +    ++  -    ++   0   0   0                                           284                                                                               -    +++  ++  -    +    0   0   0                                           285                                                                               -    -    -   -    -    0   0   0                                           286                                                                               +    -    +   -    -    0   0   0                                           287                                                                               -    -    +   -    ++   0   0   0                                           288                                                                               -    +    -   -    +    0   0   0                                           289                                                                               +    ++   ++  -    +++  0   0   0                                           290                                                                               -    +++  +   -    +++  0   0   0                                           291                                                                               +++  +++  +++ -    +++  0   0   0                                           292                                                                               -    -    -   -    -    0   0   0                                           293                                                                               -    -    ++  -    -    0   0   0                                           294                                                                               -    -    -   -    -    0   0   0                                           295                                                                               +    +    +   -    ++   0   0   0                                           296                                                                               -    ++   ++  -    +    0   0   0                                           297                                                                               +++  ++   +++ -    +++  0   0   0                                           298                                                                               -    -    -   -    -    0   0   0                                           299                                                                               +    ++   +++ -    ++   0   0   0                                           300                                                                               +    +++  +++ -    +++  0   0   0                                           301                                                                               -    -    +++ -    +++  0   0   0                                           302                                                                               +++  +++  +++ -    +++  0   0   0                                           303                                                                               +++  +++  +++ -    +++  0   0   0                                           304                                                                               +    +++  +++ -    +++  0   0   0                                           305                                                                               +    +    -   -    +    0   0   0                                           306                                                                               +    +++  +++ -    +++  0   0   0                                           307                                                                               -    -    +   -    -    0   0   0                                           308                                                                               +    +++  +++ -    +++  0   0   0                                           309                                                                               +    +++  +++ -    +++  0   0   0                                           310                                                                               -    ++   -   -    -    0   0   0                                           311                                                                               +    -    ++  -    ++   0   0   0                                           312                                                                               ++   -    +++ -    +++  0   0   0                                           317                                                                               ++   +++  +++ -    +++  0   0   0                                           318                                                                               -    ++   ++  -    -    0   0   0                                           319                                                                               +++  +++  +++ -    ++   0   0   0                                           320                                                                               +    +    ++  -    +    0   0   0                                           321                                                                               -    +    ++  -    -    0   0   0                                           322                                                                               +++  +++  +++ -    +    0   0   0                                           323                                                                               +    ++   +++ -    -    0   0   0                                           324                                                                               -    -    +   -    +    0   0   0                                           325                                                                               ++   ++   +++ -    +++  0   0   0                                           326                                                                               -    +    +   -    -    0   0   0                                           327                                                                               +++  -    ++  -    +++  0   0   0                                           328                                                                               +    -    +++ -    +++  0   0   0                                           __________________________________________________________________________

Field Tests

Selected compounds were field tested against a variety of plant pathogens. The following table reports pathogens against which compounds of the invention showed activity in these tests.

                  TABLE 14                                                         ______________________________________                                         COMPOUND                                                                       EX. NO.   CROP      PATHOGEN                                                   ______________________________________                                         2         barley    Pyrenophora teres                                                    potato    Phytophthora infestans                                               tomato    Phytophthora infestans                                     5         barley    Pyrenophora teres                                                              Rhynchosporium secalis                                               cucumber  Sphaerotheca fuliginea                                               grape     Plasmopara viticola                                                  potato    Phytophthora infestans                                               rape      Alternaria brassica                                                  tomato    Phytophthora infestans                                     10        barley    Rhynchosporium secalis                                                         Pyrenophora teres                                                              Erysiphe graminis hordei                                             cucumber  Sphaerotheca fuliginea                                               wheat     Pseudocercosporella herpotrichoides                                            Erysiphe graminis tritici                                  97        grape     Plasmopara viticola                                        159       barley    Rhynchosporium secalis                                               grape     Plasmopara viticola                                                  wheat     Puccinia recondita                                         173       grape     Plasmopara viticola                                        200       barley    Rhynchosporium secalis                                                         Pyrenophora teres                                                              Erysiphe graminis hordei                                             cucumber  Sphaerotheca fuliginea                                               wheat     Pseudocercosporella herpotrichoides                                            Erysiphe graminis tritici                                  212       apple     Podosphaera leucotricha                                              barley    Pyrenophora teres                                                    grape     Uncinula necator                                                               Plasmopara viticola                                                  rape      Alternaria brassica                                                  rice      Piricularia oryzae                                         212       barley    Rhynchosporium secalis                                                         Pyrenophora teres                                                              Erysiphe graminis hordei                                             cucumber  Sphaerotheca fuliginea                                               wheat     Pseudocercosporella herpotrichoides                                            Erysiphe graminis tritici                                  219       barley    Rhynchosporium secalis                                                         Pyrenophora teres                                                              Erysiphe graminis hordei                                             cucumber  Sphaerotheca fuliginea                                               wheat     Pseudocercosporella herpotrichoides                                            Erysiphe graminis tritici                                  221       sugar beet                                                                               Erysiphe sp.                                               ______________________________________                                    

Combinations

Fungal disease pathogens are known to develop resistance to fungicides. When strains resistant to a fungicide do develop, it becomes necessary to apply larger and larger amounts of the fungicide to obtain desired results. To retard the development of resistance to new fungicides, it is desirable to apply the new fungicides in combination with other fungicides. Use of a combination product also permits the product's spectrum of activity to be adjusted.

Accordingly, another aspect of the invention is a fungicidal combination comprising at least 1% by weight of a compound of formula (1) in combination with a second fungicide.

Contemplated classes of fungicides from which the second fungicide may be selected include:

1) N-substituted azoles, for example propiconazole, triademefon, flusilazol, diniconazole, ethyltrianol, myclobutanil, and prochloraz;

2) pyrimidines, such as fenarimol and nuarimol;

3) morpholines, such as fenpropimorph and tridemorph;

4) piperazines, such as triforine; and

5) pyridines, such as pyrifenox. Fungicides in these five classes all function by inhibiting sterol biosynthesis. Additional classes of contemplated fungicides, which have other mechanisms of action, include:

6) dithiocarbamates, such as maneb and mancozeb;

7) phthalimides, such as captafol;

8) isophthalonitrites, such as chlorothalonil;

9) dicarboximides, such as iprodione;

10) benzimidazoles, such as benomyl and carbendazim;

11) 2-aminopyrimidines, such as ethirimol;

12) carboxamides, such as carboxin; and

13) dinitrophenols, such as dinocap.

The fungicide combinations of the invention contain at least 1%, ordinarily 20 to 80%, and more typically 50 to 75% by weight of a compound of formula (1).

Combination Tests

Selected compounds were tested in the greenhouse in combination with other known fungicides against various plant pathogens. Results are reported in Tables 15 and 16. In the tables, the time given under "Time in hours" is the number of hours elapsing between treatment and inoculation. A negative time indicates that the pathogen was inoculated before treatment. In such cases, curative activity was being tested. A positive time indicates that the plants were treated before they were inoculated with pathogen. In such cases, residual or protectant activity was tested. The compounds were formulated and applied as foliar sprays as in Test 1. The results were evaluated on a 1-9 rating scale. These ratings represent the following percent disease control:

1=0-19%, 2=20-29%, 3=30-39%, 4=40-59%, 5=60-74%,

6=75-89%, 7=90-96%, 8=97-99%, and 9=100%.

                  TABLE 15                                                         ______________________________________                                         CUCURBIT DOWNY MILDEW                                                          COMPOUND 1            RATE     RATE                                            PLUS       TIME       CMPD 1   CMPD 2 RE-                                      COMPOUND 2 IN HOURS   IN PPM   IN PPM SULTS                                    ______________________________________                                         Ex. 5      4          48.00           8.0                                                            24.00           7.5                                                            12.00           7.0                                                            6.00            1.0                                      nuarimol   4          2.00            1.0                                                            1.00            1.0                                                            0.50            1.0                                                            0.25            1.0                                      nuarimol + Ex. 5                                                                          4          2.00     48.00  8.5                                                            1.00     24.00  7.5                                                            0.50     12.00  5.0                                                            0.25      6.00  1.0                                      ______________________________________                                    

                  TABLE 16                                                         ______________________________________                                         CUCURBIT POWDERY MILDEW                                                        ______________________________________                                         Ex. 5         4     48.00           6.0                                                            24.00           5.0                                                            12.00           1.0                                                            6.00            1.0                                        nuarimol      4     2.00            9.0                                                            1.00            8.0                                                            0.50            7.0                                                            0.25            6.0                                        nuarimol + Ex. 5                                                                             4     2.00       48.00                                                                               9.0                                                            1.00       24.00                                                                               9.0                                                            0.50       12.00                                                                               8.0                                                            0.25        6.00                                                                               6.0                                        ______________________________________                                    

Insecticide and Miticide Utility

The compounds of the invention are also useful for the control of insects and mites. Therefore, the present invention also is directed to a method for inhibiting an insect or mite which comprises applying to a locus of the insect or mite an insect- or mite-inhibiting amount of a compound of formula (1).

The compounds of the invention show activity against a number of insects and mites. More specifically, the compounds show activity against melon aphid, which is a member of the insect order Homoptera. Other members of the Homoptera include leafhoppers, planthoppers, pear pyslla, apple sucker, scale insects, whiteflies, spittle bugs as well as numerous other host specific aphid species. Activity has also been observed against greenhouse thrips, which are members of the order Thysanoptera. The compounds also show activity against Southern armyworm, which is a member of the insect order Lepidoptera. Other typical members of this order are codling moth, cutworm, clothes moth, Indianmeal moth, leaf rollers, corn earworm, European corn borer, cabbage worm, cabbage looper, cotton bollworm, bagworm, eastern tent caterpillar, sod webworm, and fall armyworm.

Representative mite species with which it is contemplated that the present invention can be practiced include those listed below.

    __________________________________________________________________________     FAMILY      SCIENTIFIC NAME                                                                              COMMON NAME                                          __________________________________________________________________________     ACARIDAE    Aleurobius farinae                                                             Rhizoglyphus echinopus                                                                       Bulb mite                                                        Rhizoglyphus elongatus                                                         Rhizoglyphus rhizophagus                                                       Rhizoglyphus sagittatae                                                        Rhizoglyphus tarsalis                                              ERIOPHYIDAE Abacarus farinae                                                                             Grain rust mite                                                  Aceria brachytarsus                                                            Acalitus essigi                                                                              Redberry mite                                                    Aceria ficus                                                                   Aceria fraaxinivorus                                                           Aceria granati                                                                 Aceria parapopuli                                                              Eriophyes sheldoni                                                                           Citrus bud mite                                                  Aceria tulipae                                                                 Aculus carnutus                                                                              Peach silver mite                                                Aculus schlechtendali                                                                        Apple rust mite                                                  Colomerus vitis                                                                              Grape erineum mite                                               Eriophyes convolvens                                                           Eriophyes insidiosus                                                           Eriophyes malifoliae                                                           Eriophyes padi                                                                 Eriophyes pruni                                                                Epitrimerus pyri                                                                             Pear leaf blister mite                                           Eriophyes ramosus                                                              Eriophyes sheldoni                                                                           Citrus bud mite                                                  Eriophyes ribis                                                                Phyllocoptes gracilis                                                                        Dryberry mite                                                    Phyllocoptruta oleivora                                                                      Citrus rust mite                                                 Phytoptus ribis                                                                Trisetacus pini                                                                Vasates amygdalina                                                             Vasates eurynotus                                                              Vasates quadripedes                                                                          Maple bladdergall mite                                           Vasates schlechtendali                                             EUPODIDAE   Penthaleus major                                                                             Winter grain mite                                                Linopodes spp.                                                     NALEPELLIDAE                                                                               Phylocoptella avellanae                                                                      Filbert bud mite                                     PENTHALEIDAE                                                                               Halotydeus destrustor                                              PYEMOTIDAE  Pyemotes tritici                                                                             Straw itch mite                                                  Siteroptes cerealium                                               TARSONEMIDAE                                                                               Polyphagotarsonemus latus                                                                    Broad mite                                                       Steneotarsonemus pallidus                                                                    Cyclamen mite                                        TENUIPALPIDAE                                                                              Brevipalpus californicus                                                       Brevipalpus obovatus                                                                         Privet mite                                                      Brevipalpus lewisi                                                                           Citrus flat mite                                                 Dolichotetranychus floridanus                                                                Pineapple flase spider                                                         mite                                                             Tenuipalpes granati                                                            Tenuipalpes pacificus                                              TETRANYCHIDAE                                                                              Bryobia arborea                                                                Bryobia practiosa                                                                            Clover mite                                                      Bryobia rubrioculus                                                                          Brown mite                                                       Eotetranychus coryli                                                           Eotetranychus hicoriae                                                                       Pecan deaf scorch mite                                           Eotetranychus lewisi                                                           Eotetranychus sexmaculatus                                                                   Sixspotted spider mite                                           Eotetranychus willametti                                                       Eotetranychus banksi                                                                         Texas citrus mite                                                Oligonychus ilicis                                                                           Southern red mite                                                Oligonychus pratensis                                                                        Banks grass mite                                                 Oligonychus ununguis                                                                         Spruce spider mite                                               Panonychus citri                                                                             Citrus red mite                                                  Panonychus ulmi                                                                              European red mite                                                Paratetranychus modestus                                                       Paratetranychus pratensis                                                      Paratetranychus viridis                                                        Petrobia latens                                                                              Brown wheat mite                                                 Schizotetranychus celarius                                                                   Bamboo spider mite                                               Schizotetranychus pratensis                                                    Tetranychus canadensis                                                                       Fourspotted spider mite                                          Tetranychus cinnabarinus                                                                     Carmine spider mite                                               Tetranychus mcdanieli                                                                       McDaniel spider mite                                             Tetranychus pacificus                                                                        Pacific spider mite                                              Tetranychus schoenei                                                                         Schoene spider mite                                              Tetranychus urticae                                                                          Twospotted spider mite                                           Tetranychus turkestani                                                                       Strawberry spider mite                                           Tetranychus desertorum                                                                       Desert spider mite                                   __________________________________________________________________________

The compounds are useful for reducing populations of insects and mites, and are used in a method of inhibiting an insect or mite population which comprises applying to a locus of the insect or arachnid an effective insect- or mite-inactivating amount of a compound of formula (1). The "locus" of insects or mites is a term used herein to refer to the environment in which the insects or mites live or where their eggs are present, including the air surrounding them, the food they eat, or objects which they contact. For example, plant-ingesting insects or mites can be controlled by applying the active compound to plant parts, which the insects or mites eat, particularly the foliage. It is contemplated that the compounds might also be useful to protect textiles, paper, stored grain, or seeds by applying an active compound to such substance. The term "inhibiting an insect or mite" refers to a decrease in the numbers of living insects or mites; or a decrease in the number of viable insect or mite eggs. The extent of reduction accomplished by a compound depends, of course, upon the application rate of the compound, the particular compound used, and the target insect or mite species. At least an insect-inactivating or mite-inactivating amount should be used. The terms "insect-inactivating amount" and "mite-inactivating amount" are used to describe the amount, which is sufficient to cause a measurable reduction in the treated insect or mite population. Generally an amount in the range from about 1 to about 1000 ppm active compound is used.

In a preferred embodiment, the present invention is directed to a method for inhibiting a mite which comprises applying to a plant an effective mite-inactivating amount of a compound of formula (1) in accordance with the present invention.

MITE/INSECT SCREEN

The compounds of Examples 1-295 were tested for miticidal and insecticidal activity in the following mite/insect screen.

Each test compound was formulated by dissolving the compound in acetone/alcohol (50:50) mixture containing 23 g of "TOXIMUL R" (sulfonate/nonionic emulsifier blend) and 13 g of "TOXIMUL S" (sulfonate/nonionic emulsifier blend) per liter. These mixtures were then diluted with water to give the indicated concentrations.

Twospotted spider mites (Tetranychus urticae Koch) and melon aphids (Aphis gossypii Glover) were introduced on squash cotyledons and allowed to establish on both leaf surfaces. Other plants in the same treatment pot were left uninfested. The leaves were then sprayed with 5 ml of test solution using a DeVilbiss atomizing sprayer at 10 psi. Both surfaces of the leaves were covered until runoff, and then allowed to dry for one hour. Two uninfested leaves were then excised and placed into a Petri dish containing southern armyworm (Spodopetra eridania Cramer).

After standard exposure periods, percent mortality was evaluated. Results are reported in Table 17, where the following abbreviations are used.

CRW refers to corn rootworm

SAW refers to Southern armyworm

SM refers to twospotted spider mites

MA refers to melon aphids.

                                      TABLE 17                                     __________________________________________________________________________     MITE/INSECT SCREEN                                                                               SAW                                                                  CRW CRW   SM & MA                                                                              SAW   SM    MA                                         COMPOUND                                                                               RATE                                                                               RESULTS                                                                              RATE  RESULTS                                                                              RESULTS                                                                              RESULTS                                    EX. NO. PPM %     PPM   %     %     %                                          __________________________________________________________________________     1       12.00                                                                              0     200   0     0     0                                          2       12.00                                                                              0     200   0     0     0                                          3       12.00                                                                              0     200   0     0     0                                          4       12.00                                                                              0     200   0     0     0                                          5       12.00                                                                              0     200   0     0     0                                          6       12.00                                                                              0     200   0     0     0                                          7       12.00                                                                              0     200   0     0     0                                          8       12.00                                                                              0     200   100   0     0                                          9       12.00                                                                              0     200   0     0     0                                          10      12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          11      24.00                                                                              60    400   100   0     0                                                  12.00                                                                              0     200   80    0     0                                          12      24.00                                                                              40    400   100   0     0                                                  12.00                                                                              0     200   0     0     0                                          13      24.00                                                                              0     400   0     0     0                                                  12.00                                                                              0     200   0     0     0                                          14      24.00                                                                              0     400   0     0     0                                                  12.00                                                                              0     200   0     0     0                                          15      24.00                                                                              0     400   0     0     0                                                  12.00                                                                              0     200   0     0     0                                          16      12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          17      12.00                                                                              0     200   0     0     0                                          18      12.00                                                                              0     200   0     0     0                                          19      12.00                                                                              0     200   0     0     0                                          20      12.00                                                                              0     200   0     0     0                                          21      12.00                                                                              0     200   0     0     0                                          22      12.00                                                                              0     200   0     0     0                                          23      12.00                                                                              0     200   0     0     0                                          24      12.00                                                                              0     200   0     0     0                                          25      12.00                                                                              0     200   0     0     0                                          26      12.00                                                                              0     200   0     0     0                                          27      12.00                                                                              0     200   0     0     0                                          28      12.00                                                                              0     200   0     0     0                                          29      12.00                                                                              0     200   0     0     0                                          30      12.00                                                                              0     200   0     0     0                                          31      12.00                                                                              0     200   0     0     0                                          32      12.00                                                                              0     200   0     0     0                                          33      12.00                                                                              0     200   0     0     0                                          34      12.00                                                                              0     200   0     0     0                                          35      12.00                                                                              0     200   0     0     0                                          36      12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          37      12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          38      12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          39      24.00                                                                              0     400   0     0     0                                                  12.00                                                                              0     200   0     0     0                                          40      24.00                                                                              100   400   80    0     0                                                  12.00                                                                              0     200   0     0     0                                          41      24.00                                                                              0     400   40    0     0                                                  12.00                                                                              0     200   80    0     0                                          42      24.00                                                                              0     400   0     0     0                                                  12.00                                                                              0     200   0     0     0                                          43      24.00                                                                              0     400   0     0     0                                                  12.00                                                                              0     200   0     0     0                                          44      24.00                                                                              0     400   0     0     0                                                  12.00                                                                              0     200   0     0     0                                          45      12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          46      12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          47      12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          48      12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          49      12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          50      12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          51      12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   20    0     0                                          52      12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          53      12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          54      12.00                                                                              0     200   0     0     0                                          55      12.00                                                                              0     200   0     0     0                                          56      24.00                                                                              0     400   80    0     0                                                  12.00                                                                              0     200   100   0     0                                          57      12.00                                                                              0     200   40    0     0                                                  24.00                                                                              0     400   50    0     0                                          58      24.00                                                                              0     400   0     0     0                                          59      24.00                                                                              0     400   0     0     0                                                  12.00                                                                              0     200   0     0     0                                          60      24.00                                                                              0     400   0     0     0                                                  12.00                                                                              0     200   0     0     0                                          61      24.00                                                                              0     400   0     0     0                                                  12.00                                                                              0     200   0     0     0                                          62      24.00                                                                              0     400   0     0     0                                          63      24.00                                                                              0     400   0     0     0                                          64      24.00                                                                              0     400   0     0     0                                                  12.00                                                                              0     200   60    0     0                                          65      12.00                                                                              0     200   0     0     0                                          66      12.00                                                                              0     200   0     0     0                                          67      12.00                                                                              0     200   0     0     0                                          68      12.00                                                                              0     200   0     0     0                                          69      12.00                                                                              0     200   0     0     0                                          70      12.00                                                                              0     200   0     0     0                                          71      12.00                                                                              0     200   0     0     0                                                  12.00                                                                              60    200   0     0     0                                          72      24.00                                                                              0     400   0     0     0                                          73      12.00                                                                              0     200   0     0     0                                          74      12.00                                                                              0     200   20    0     0                                                  12.00                                                                              0     200   0     0     0                                          75      12.00                                                                              0     200   0     0     0                                          76      12.00                                                                              0     200   0     0     0                                                  12.00                                                                              0     200   90    0     0                                          77      12.00                                                                              0     200   0     0     0                                          78      12.00                                                                              0     200   20    0     0                                                  12.00                                                                              0     200   20    0     0                                          79      12.00                                                                              0     200   10    0     0                                                  12.00                                                                              0     200   60    0     0                                          80      12.00                                                                              0     200   0     0     0                                          81      12.00                                                                              0     200   0     0     0                                          82      12.00                                                                              0     200   0     0     0                                          83      12.00                                                                              0     200   0     0     0                                          84      12.00                                                                              0     200   10    0     0                                                  24.00                                                                              0     400   0     0     0                                          85      12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          86      12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          87      12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          88      24.00                                                                              0     400   0     0     0                                                  12.00                                                                              0     200   0     0     0                                          89      24.00                                                                              0     400   0     0     0                                                  12.00                                                                              0     200   0     0     0                                          90      24.00                                                                              0     400   0     0     0                                                  12.00                                                                              0     200   100   80    80                                         91      12.00                                                                              0     200   0     0     0                                          92      12.00                                                                              0     200   0     0     0                                          93      12.00                                                                              0     200   0     0     0                                          94      12.00                                                                              100   200   0     0     0                                          95      12.00                                                                              0     200   20    0     0                                                  12.00                                                                              0     200   40    0     0                                          96      12.00                                                                              0     200   100   0     0                                                  12.00                                                                              0     200   100   0     0                                          97      12.00                                                                              0     200   0     0     0                                          98      12.00                                                                              0     200   0     0     0                                          99      12.00                                                                              0     200   0     0     0                                          100     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          101     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          102     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   50    0     0                                          103     24.00                                                                              0     400   0     0     0                                                  12.00                                                                              0     200   0     0     0                                          104     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   60    0     0                                          105     12.00                                                                              0     200   30    100   80                                                 24.00                                                                              0     400   0     0     50                                         106     24.00                                                                              0     400   0     0     0                                          107     24.00                                                                              0     400   0     0     0                                                  12.00                                                                              0     200   0     0     0                                          108     12.00                                                                              0     200   0     0     0                                          109     24.00                                                                              0     400   0     0     0                                          110     24.00                                                                              0     400   0     0     0                                                  12.00                                                                              0     200   0     0     0                                          111     12.00                                                                              0     200   20    90    0                                                  24.00                                                                              0     400   20    80    0                                          112     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          113     12.00                                                                              0     200   100   40    0                                                  24.00                                                                              100   400   70    0     0                                          114     24.00                                                                              0     400   70    100   30                                         115     24.00                                                                              0     400   0     0     0                                                  12.00                                                                              0     200   0     0     0                                          116     12.00                                                                              0     200   0     0     0                                          117     12.00                                                                              0     200   0     0     0                                                  12.00                                                                              0     200   0     0     0                                          118     12.00                                                                              0     200   0     0     0                                          119     12.00                                                                              0     200   0     0     0                                          120     12.00                                                                              0     200   0     0     0                                          121     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          122     24.00                                                                              0     400   0     0     0                                                  12.00                                                                              0     200   0     0     0                                          123     12.00                                                                              0     200   0     0     0                                          124     24.00                                                                              0     400   0     0     0                                                  12.00                                                                              0     200   0     0     0                                          125     24.00                                                                              0     400   0     0     0                                                  12.00                                                                              0     200   0     0     0                                          126     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          127     24.00                                                                              0     400   0     0     0                                                  12.00                                                                              0     200   0     0     0                                          128     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          129     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          130     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          131     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          132     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          133     24.00                                                                              0     400   0     0     0                                                  12.00                                                                              0     200   0     0     0                                          134     24.00                                                                              0     400   0     0     0                                          135     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          136     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          137     24.00                                                                              0     400   100   80    80                                         138     24.00                                                                              0     400   0     0     0                                          139     12.00                                                                              0     200   0     0     0                                          140     24.00                                                                              0     400   60    0     0                                                  12.00                                                                              0     200   0     0     0                                          141     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          142     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          143     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          144     24.00                                                                              0     400   0     0     0                                                  12.00                                                                              0     200   0     0     0                                          145     24.00                                                                              0     400   0     0     0                                                  12.00                                                                              0     200   0     0     0                                          146     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          147     12.00                                                                              0     200   0     0     0                                          148     12.00                                                                              0     200   0     0     0                                          149     12.00                                                                              0     200   0     0     0                                          150     12.00                                                                              0     200   0     0     0                                                  12.00                                                                              0     200   0     0     0                                          151     12.00                                                                              0     200   0     0     0                                          152     12.00                                                                              0     200   0     0     0                                                  12.00                                                                              0     200   0     0     0                                          153     12.00                                                                              0     200   0     0     0                                          154     12.00                                                                              0     200   0     0     0                                                  12.00                                                                              0     200   0     0     0                                          155     12.00                                                                              0     200   0     0     0                                          156     12.00                                                                              0     200   0     0     0                                                  12.00                                                                              0     200   0     0     0                                          157     24.00                                                                              0     400   100   80    0                                          158     12.00                                                                              0     200   0     0     0                                          159     12.00                                                                              0     200   0     0     0                                          160     24.00                                                                              0     400   0     0     0                                                  12.00                                                                              0     200   0     0     0                                          161     24.00                                                                              40    400   0     0     80                                                 12.00                                                                              0     200   0     0     0                                          162     12.00                                                                              0     200   0     0     0                                          163     12.00                                                                              0     200   0     0     0                                          164     12.00                                                                              0     200   0     0     0                                          165     24.00                                                                              0     400   0     0     0                                                  12.00                                                                              0     200   0     0     0                                          166     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          167     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          168     24.00                                                                              0     400   0     0     0                                                  12.00                                                                              0     200   0     0     0                                          169     24.00                                                                              0     400   0     0     0                                                  12.00                                                                              0     200   0     0     0                                          170     12.00                                                                              0     200   0     0     0                                          171     12.00                                                                              0     200   0     0     0                                          172     12.00                                                                              0     200   0     0     0                                          173     12.00                                                                              0     200   0     0     0                                          174     12.00                                                                              0     200   0     0     0                                          175     12.00                                                                              0     200   0     0     0                                          176     12.00                                                                              0     200   0     0     0                                          177     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              100   400   0     0     0                                          178     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          179     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          180     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          181     12.00                                                                              0     200   0     0     0                                          182     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          183     12.00                                                                              0     200   0     0     0                                          184     12.00                                                                              0     200   0     0     0                                          185     24.00                                                                              0     400   0     0     0                                                  12.00                                                                              0     200   0     0     0                                          186     24.00                                                                              0     400   0     0     0                                                  12.00                                                                              0     200   0     0     0                                          187     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          188     24.00                                                                              0     400   0     0     0                                          189     12.00                                                                              0     200   0     0     0                                          190     12.00                                                                              0     200   0     0     0                                          191     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          192     24.00                                                                              0     400   0     0     0                                                  12.00                                                                              0     200   0     0     0                                          193     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          194     24.00                                                                              0     400   0     0     0                                                  12.00                                                                              0     200   0     0     0                                          195     24.00                                                                              0     400   0     0     0                                          196     24.00                                                                              0     400   0     100   100                                        197     24.00                                                                              0     400   80    90    80                                         198     24.00                                                                              0     400   0     90    80                                         199     24.00                                                                              100   400   0     0     0                                          200     24.00                                                                              0     400   50    100   100                                                12.00                                                                              0     200   0     100   100                                        201     12.00                                                                              0     200   0     80    100                                                24.00                                                                              0     400   0     80    100                                        202     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          203     12.00                                                                              0     200   10    0     100                                                24.00                                                                              0     400   0     0     90                                         204     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   100   0     50                                         205     24.00                                                                              0     400   0     0     0                                          206     24.00                                                                              0     400   0     0     0                                          207     12.00                                                                              0     200   0     0     0                                          208     12.00                                                                              0     200   0     10    10                                         209     12.00                                                                              0     200   10    0     0                                                  12.00                                                                              0     200   100   0     40                                         210     12.00                                                                              0     200   0     0     0                                          211     12.00                                                                              0     200   0     10    40                                         212     12.00                                                                              0     200   0     0     0                                          213     12.00                                                                              0     200   0     0     0                                          214     24.00                                                                              0     400   0     0     0                                          2115    24.00                                                                              0     400   0     100   100                                        216     24.00                                                                              100   400   0     0     0                                          217     24.00                                                                              0     400   0     0     0                                          218     24.00                                                                              0     400   100   0     0                                          219     12.00                                                                              0     200   0     0     0                                          220     24.00                                                                              0     400   0     0     0                                                  12.00                                                                              0     200   0     0     0                                          221     24.00                                                                              0     400   0     90    80                                                 12.00                                                                              40    200   0     90    90                                         222     24.00                                                                              0     400   0     0     40                                                 12.00                                                                              0     200   0     0     50                                         223     24.00                                                                              0     400   0     0     100                                                12.00                                                                              80    200   0     0     80                                         224     24.00                                                                              0     400   0     0     0                                          225     24.00                                                                              0     400   0     0     0                                          226     24.00                                                                              0     400   0     0     0                                                  12.00                                                                              0     200   0     0     0                                          227     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          228     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     80                                         229     12.00                                                                              0     200   0     50    50                                                 24.00                                                                              0     400   0     0     0                                          230     12.00                                                                              0     200   0     100   90                                                 24.00                                                                              0     400   0     80    0                                          231     12.00                                                                              0     200   0     90    0                                                  24.00                                                                              0     400   0     40    50                                         232     24.00                                                                              0     400   30    80    40                                                 12.00                                                                              0     200   0     100   70                                         233     12.00                                                                              0     200   0     100   50                                                 24.00                                                                              0     400   0     80    80                                         234     12.00                                                                              0     200   60    50    50                                                 24.00                                                                              0     400   0     30    100                                        235     24.00                                                                              0     400   0     0     50                                                 12.00                                                                              0     200   80    0     0                                          236     24.00                                                                              40    400   0     0     30                                                 12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          237     24.00                                                                              0     400   0     100   0                                                  12.00                                                                              0     200   0     0     0                                          238     24.00                                                                              0     400   100   0     0                                                  12.00                                                                              0     200   0     100   100                                        239     24.00                                                                              0     400   0     0     0                                                  12.00                                                                              0     200   0     0     0                                          240     24.00                                                                              0     400   0     0     0                                          241     24.00                                                                              0     400   0     0     0                                          242     24.00                                                                              0     400   0     0     0                                                  12.00                                                                              0     200   0     0     0                                          243     24.00                                                                              0     400   0     0     0                                          244     12.00                                                                              0     200   0     0     40                                         245     12.00                                                                              0     200   0     0     0                                          246     12.00                                                                              0     200   0     0     0                                          247     24.00                                                                              0     400   50    0     0                                                  12.00                                                                              0     200   20    90    0                                          248     24.00                                                                              0     400   0     0     0                                          249     24.00                                                                              0     400   0     0     0                                          250     24.00                                                                              0     400   0     0     0                                          251     12.00                                                                              0     200   0     0     0                                          252     24.00                                                                              0     400   0     90    100                                                12.00                                                                              0     200   0     90    100                                        253     24.00                                                                              0     400   0     100   100                                                12.00                                                                              0     200   0     100   90                                         254     24.00                                                                              0     400   0     0     0                                          255     24.00                                                                              0     400   0     0     0                                          256     24.00                                                                              100   400   100   0     0                                          257     24.00                                                                              0     400   0     0     0                                          258     24.00                                                                              0     400   0     90    100                                        259     24.00                                                                              0     400   0     80    80                                                 12.00                                                                              0     200   0     100   90                                         260     24.00                                                                              40    400   40    0     0                                                  12.00                                                                              0     200   100   100   100                                        261     24.00                                                                              100   400   80    50    100                                                12.00                                                                              0     200   100   90    100                                        262     12.00                                                                              0     200   0     100   100                                                24.00                                                                              0     400   0     100   100                                        263     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          264     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          265     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          266     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          267     12.00                                                                              0     200   0     40    20                                                 24.00                                                                              0     400   0     100   100                                        268     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     80    0                                          269     12.00                                                                              0     200   0           30                                                 24.00                                                                              40    400   0     0     0                                          270     12.00                                                                              0     200   20    0     0                                                  24.00                                                                              0     400   0     80    0                                          271     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          272     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     20    0                                          273     24.00                                                                              0     400   0     0     0                                          274     12.00                                                                              0     200   0     100   100                                                24.00                                                                              0     400   0     0     100                                        275     12.00                                                                              0     200   0     0     90                                                 24.00                                                                              0     400   0     60    100                                        276     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     60    80                                         277     24.00                                                                              0     400   0     0     0                                          278     12.00                                                                              0     200   0     60    90                                                 24.00                                                                              0     400   100   0     0                                          279     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     80                                         280     12.00                                                                              0     200   60    0     0                                                  24.00                                                                              0     400   0     0     0                                          281     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          282     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          283     12.00                                                                              0     200   0     0     80                                                 24.00                                                                              0     400   0     80    0                                          284     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          285     12.00                                                                              0     200   0     40    80                                                 24.00                                                                              0     400   0     0     0                                          286     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          287     12.00                                                                              0     200   0     0     80                                                 24.00                                                                              0     400   0     0     0                                          288     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          289     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          290     12.00                                                                              0     200   0     80    80                                                 24.00                                                                              0     400   0     0     0                                          291     12.00                                                                              0     200   0     0     100                                                24.00                                                                              0     400   0     0     0                                          292     12.00                                                                              0     200   0     0     30                                                 24.00                                                                              0     400   0     0     0                                          293     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          294     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          295     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          296     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     80                                         297     12.00                                                                              0     200   100   100   100                                                24.00                                                                              0     400   100   100   100                                        298     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          299     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          300     12.00                                                                              0     200   20    0     0                                                  24.00                                                                              0     400   0     0     0                                          301     12.00                                                                              0     200   40    0     0                                                  24.00                                                                              0     400   0     0     0                                          302     12.00                                                                              0     200   100   100   100                                                24.00                                                                              0     400   0     0     100                                        303     12.00                                                                              0     200   0     100   100                                                24.00                                                                              0     400   0     0     100                                        304     12.00                                                                              0     200   0     100   100                                                24.00                                                                              0     400   0     100   80                                         305     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          306     12.00                                                                              0     200   0     100   100                                                24.00                                                                              100   400   100   0     0                                          307     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          308     12.00                                                                              0     200   0     0     80                                                 24.00                                                                              0     400   0     0     80                                         309     12.00                                                                              0     200   0     40    60                                                 24.00                                                                              0     400   100   0     0                                          310     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     90                                         311     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     40                                         312     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          313     12.00     200                                                                  24.00                                                                              0     400   0     30    0                                          314     24.00                                                                              100   400   0     100   100                                        317     12.00                                                                              0     200   80    80    80                                                 24.00                                                                              0     400   0     0     60                                         318     12.00     200                                                                  24.00                                                                              0     400   0     0     0                                          319     12.00     200                                                                  24.00                                                                              0     400   0     100   100                                        320     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          321     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          322     12.00                                                                              0     200   60    100   80                                                 24.00                                                                              0     400   60    80    100                                        323     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          324     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          325     12.00                                                                              0     200   0     0     80                                                 24.00                                                                              0     400   80    0     0                                          326     12.00                                                                              0     200   0     0     0                                                  24.00                                                                              0     400   0     0     0                                          327     12.00                                                                              0     200   80    0     100                                                24.00                                                                              60    400   0     80    60                                         328     12.00                                                                              100   200   100   80    80                                                 24.00                                                                              100   400   100   0     0                                          __________________________________________________________________________

Field Trips

4-[2-]4-(t-Butyl)phenyl]ethoxy]-8-fluoroquinoline (Example 221) was evaluated in a number of field trials. The following table reports the host plants on which it was tested and the pest species against which it showed activity.

                  TABLE 18                                                         ______________________________________                                         HOST            PEST                                                           ______________________________________                                         alfalfa (Lucerne)                                                                              pea aphid, potato leaf hopper,                                                 tarnished plant bug, green                                                     cloverworm                                                     apples          mites, apple aphid, European red                                               mite, green peach aphid, white                                                 apple leafhopper, apple rust mite,                                             rosy apple aphid                                               azaleas         greenhouse thrip                                               bean, faba broad                                                                               bean aphid                                                     broccoli        twospotted spider mite                                         cotton          cotton aphid                                                   grape (European)                                                                               grape thrip, grape leafhopper                                  hops            Dawson-hop aphid                                               pea, garden (English)                                                                          pea aphid                                                      pecan nut       yellow hickory aphid                                           privet          thrip                                                          sugar beet      green peach aphid                                              wheat           wheat aphid                                                    ______________________________________                                    

Compositions

The compounds of this invention are applied in the form of compositions which are important embodiments of the invention, and which comprise a compound of this invention and a phytologically-acceptable inert carrier. The compositions are either concentrated formulations which are dispersed in water for application, or are dust or granular formulations which are applied without further treatment. The compositions are prepared according to procedures and formulae which are conventional in the agricultural chemical art, but which are novel and important because of the presence therein of the compounds of this invention. Some description of the formulation of the compositions will be given, however, to assure that agricultural chemists can readily prepare any desired composition.

The dispersions in which the compounds are applied are most often aqueous suspensions or emulsions prepared from concentrated formulations of the compounds. Such water-soluble, water-suspendable or emulsifiable formulations are either solids usually known as wettable powders, or liquids usually known as emulsifiable concentrates or aqueous suspensions. Wettable powders, which may be compacted to form water dispersible granules, comprise an intimate mixture of the active compound, an inert carrier and surfactants. The concentration of the active compound is usually from about 10% to about 90% by weight. The inert carrier is usually chosen from among the attapulgite clays, the montmorillonite clays, the diatomaceous earths, or the purified silicates. Effective surfactants, comprising from about 0.5% to about 10% of the wettable powder, are found among the sulfonated lignins, the condensed naphthalenesulfonates, the naphthalenesulfonates, the alkylbenzenesulfonates, the alkyl sulfates, and nonionic surfactants such as ethylene oxide adducts of alkyl phenols.

Emulsifiable concentrates of the compounds comprise a convenient concentration of a compound, such as from about 50 to about 500 grams per liter of liquid, equivalent to about 10% to about 50%, dissolved in an inert carrier which is either a water miscible solvent or a mixture of water-immiscible organic solvent and emulsifiers. Useful organic solvents include aromatics, especially the xylenes, and the petroleum fractions, especially the high-boiling naphthalenic and olefinic portions of petroleum such as heavy aromatic naphtha. Other organic solvents may also be used, such as the terpenic solvents including rosin derivatives, aliphatic ketones such as cyclohexanone, and complex alcohols such as 2-ethoxyethanol. Suitable emulsifiers for emulsifiable concentrates are chosen from conventional nonionic surfactants, such as those mentioned above.

Aqueous suspensions comprise suspensions of water-insoluble compounds of this invention, dispersed in an aqueous vehicle at a concentration in the range from about 5% to about 50% by weight. Suspensions are prepared by finely grinding the compound, and vigorously mixing it into a vehicle comprised of water and surfactants chosen from the same types discussed above. Inert ingredients, such as inorganic salts and synthetic or natural gums, may also be added, to increase the density and viscosity of the aqueous vehicle. It is often most effective to grind and mix the compound at the same time by preparing the aqueous mixture, and homogenizing it in an implement such as a sand mill, ball mill, or pistontype homogenizer.

The compounds may also be applied as granular compositions, which are particularly useful for applications to the soil. Granular compositions usually contain from about 0.5% to about 10% by weight of the compound, dispersed in an inert carrier which consists entirely or in large part of clay or a similar inexpensive substance. Such compositions are usually prepared by dissolving the compound in a suitable solvent, and applying it to a granular carrier which has been pre-formed to the appropriate particle size, in the range of from about 0.5 to 3 mm. Such compositions may also be formulated by making a dough or paste of the carrier and compound, and crushing and drying to obtain the desired granular particle size.

Dusts containing the compounds are prepared simply by intimately mixing the compound in powdered form with a suitable dusty agricultural carrier, such as kaolin clay, ground volcanic rock and the like. Dusts can suitably contain from about 1% to about 10% of the compound.

It is equally practical, when desirable for any reason, to apply the compound in the form of a solution in an appropriate organic solvent, usually a bland petroleum oil, such as the spray oils, which are widely used in agricultural chemistry.

Insecticides and miticides are generally applied in the form of a dispersion of the active ingredient in a liquid carrier. It is conventional to refer to application rates in terms of the concentration of active ingredient in the carrier. The most widely used carrier is water.

The compounds of the invention can also be applied in the form of an aerosol composition. In such compositions the active compound is dissolved or dispersed in an inert carrier, which is a pressure-generating propellant mixture. The aerosol composition is packaged in a container from which the mixture is dispensed through an atomizing valve. Propellant mixtures comprise either low-boiling halocarbons, which may be mixed with organic solvents, or aqueous suspensions pressurized with inert gases or gaseous hydrocarbons.

The actual amount of compound to be applied to loci of insects and mites is not critical and can readily be determined by those skilled in the art in view of the examples above. In general, concentrations of from 10 ppm to 5000 ppm of compound are expected to provide good control. With many of the compounds, concentrations of from 100 to 1500 ppm will suffice. For field crops, such as soybeans and cotton, a suitable application rate for the compounds is about 0.5 to 1.5 lb/A, typically applied in 50 gal/A of spray formulation containing 1200 to 3600 ppm of compound. For citrus crops, a suitable application rate is from about 100 to 1500 gal/A spray formulation, which is a rate of 100 to 1000 ppm.

The locus to which a compound is applied can be any locus inhabited by an insect or arachnid, for example, vegetable crops, fruit and nut trees, grape vines, and ornamental plants. Inasmuch as many mite species are specific to a particular host, the foregoing list of mite species provides exemplification of the wide range of settings in which the present compounds can be used.

Because of the unique ability of mite eggs to resist toxicant action, repeated applications may be desirable to control newly emerged larvae, as is true of other known acaricides.

The following formulations of compounds of the invention have been prepared, and are typical of compositions useful in the practice of the present invention.

    ______________________________________                                         A. Aqueous Suspension                                                          8-Fluoro-N-[2-(2-naphthyl)ethyl]-4-quinolinamine                                                           12.5%                                              "TERGITOL TMN-6" (nonionic surfactant)                                                                     1.0%                                               "ZEOSYL 200" (silica)       1.0%                                               "AF-100" (silicon based antifoam agent)                                                                    0.2%                                               2% xanthan solution         10.0%                                              "MAKON 10" (10 moles ethyleneoxide                                                                         9.0%                                               nonylphenol surfactant)                                                        tap water                   66.3%                                              B. Emulsifiable Concentrate                                                    4-[2-[4-( .sub.-t-Butyl)phenyl]ethoxy]-8-fluoroquinoline                                                   12.4%                                              "EXXON 200" (naphthalene solvent)                                                                          83.6%                                              "TOXIMUL H" (nonionic/anionic surfactant blend)                                                            2.0%                                               "TOXIMUL D" (nonionic/anionic surfactant blend)                                                            2.0%                                               ______________________________________                                     

We claim:
 1. A compound of the formula ( 1) ##STR11## wherein: R¹ to R⁴ are independentlyH, halo, (C₁ -C₄) alkyl, branched (C₃ -C₄) alkyl, halo (C₁ -C₄) alkyl, (C₁ -C₄) alkoxy, NO₂, or NH₂, at least two of R¹ to R⁴ being H, W is CR⁵ ; R⁵ is H, CH₃, or Cl,: R⁶ is H, CH₃, Cl, or Br; A is --O--(CH₂)₂ --Ar, --NR⁷ --(CH₂)₂ --Ar, or --CR⁸ R⁹ --(CH₂)₂ --Ar; R⁷ is H, (C₁ -C₄) alkyl, or acetyl; R⁸ and R⁹ are independently H, (C₁ -C₄) alkyl, halo, or OH, or R⁸ and R⁹ combine to form a saturated or unsaturated carbocyclic ring comprising three to seven carbon atoms; and Ar is
 1. 3-benzodioxolylfluorenyl, pyridyl, substituted pyridyl, indolyl, furanyl, substituted furanyl, thienyl, optionally substituted with CH₃ or Cl, thiazolyl, cyclopentyl, 1-methylcyclopentyl, cyclohexenyl (tetrahydrophenyl), cyclohexyl (hexahydrophenyl), naphthyl, substituted naphthyl, dihydronaphthyl, tetrahydronaphthyl, decahydronaphthyl, or a group of formula (2): ##STR12## where R¹⁰ to R¹⁴ are independently H, halo, (C₁ -C₁₀) alkyl, branched (C₃ -C₆) alkyl, halo (C₁ -C₇) alkyl, (C₁ -C₇) alkoxy, halo (C₁ -C₇) alkoxy, phenoxy, substituted phenoxy, phenylthio, substituted phenylthio, phenyl, substituted phenyl, NO₂, NH₂, acetoxy, OH, CN, SiR¹⁵ R¹⁶ R¹⁷, or OSiR¹⁵ R¹⁶ R¹⁷, where R¹⁵, R¹⁶, and R¹⁷ are independently (C₁ -C₄) alkyl or (C₃ -C₄) branched alkyl, phenyl, or substituted phenyl, provided that unless each of R¹⁰ to R¹⁴ is F or CH₃, then at least two of R¹⁰ to R¹⁴ are H; or an acid addition salt of a compound of formula (1) or an N-oxide of a compound of formula (1) when W is CR⁵ where, in the foregoing definitions, the term substituted phenyl refers to phenyl substituted with up to three groups selected from halo (C₁ -C₁₀) alkyl, branched (C₃ -C₆) alkyl, halo (C₁ -C₇) alkyl, hydroxy (C₁ -C₇) alkyl, (C₁ -C₇) alkoxy, halo (C₁ -C₇) alkoxy, phenoxy, phenyl, NO₂, OH, CN, (C₁ -C₄) alkanoyloxy, or benzyloxy; the term substituted phenoxy refers to a phenoxy group substituted with up to three groups selected from halo, (C₁ -C₁₀) alkyl, branched (C₃ -C₆) alkyl, halo (C₁ -C₇) alkyl, hydroxy (C₁ -C₇) alkyl, (C₁ -C₇) alkoxy, halo (C₁ -C₇) alkoxy, phenoxy, phenyl, NO₂, OH, CN (C₁ -C₄) alkanoyloxy, or benzyloxy; the term substituted phenylthio refers to a phenylthio group substituted with up to three groups selected from halo, (C₁ -C₁₀) alkyl, branched (C₃ -C₆) alkyl, halo (C₁ -C₇) alkyl, hydroxy (C₁ -C₇) alkyl, (C₁ -C₇) alkoxy, halo (C₁ -C₇) alkoxy, phenoxy, phenyl, NO₂, OH, CN (C₁ -C₄) alkanoyloxy, or benzyloxy; the term substituted phenylsulfonyl refers to a phenylsulfonyl group substituted with up to three groups selected from halo (C₁ -C₁₀) alkyl, branched (C₃ -C₆) alkyl, halo (C₁ -C₇) alkyl, hydroxy (C₁ -C₇) alkyl, (C₁ -C₇) alkoxy, halo (C₁ -C₇) alkoxy, phenoxy, phenyl, NO₂, OH, CN (C₁ -C₄) alkanoyloxy, or benzyloxy; and the terms substituted naphthyl, substituted pyridyl, and substituted furanyl refer to these ring systems substituted with halo, halo (C₁ -C₄), CN, NO₂, (C₁ -C₄) alkyl, (C₃ -C₄) branched alkyl, phenyl, (C₁ -C₄) alkoxy, or halo (C₁ -C₄) alkoxy; provided that if A is NR⁷ --(CH₂)₂ --Ar then Ar is a group of formula (2) wherein four of R¹⁰ to R¹⁴ are H and one of R¹⁰ to R¹⁴ is Cl, (C₁ -C₄) alkyl, halo (C₁ -C₄) alkyl, branched (C₃ -C₆) alkyl, (C₁ -C₄) alkoxy, halo (C₁ -C₄) alkoxy, phenyl, substituted phenyl, phenoxy, or substituted phenoxy.
 2. A compound of claim 1 wherein W is CH.
 3. A compound of claim 1 wherein R⁶ is H.
 4. A compound of claim 1 wherein at least three of R¹ to R⁴ are H.
 5. A compound of claim 4 wherein R³ is Cl or F.
 6. A compound of claim 4 wherein R⁴ is F.
 7. A compound of claim 1 wherein A is --O--(CH₂)₂ --Ar.
 8. A compound of claim 1 wherein A is --NR⁷ --(CH₂)₂ --Ar.
 9. A compound of claim 1 wherein A is --CR⁸ R⁹ --(CH₂)₂ --Ar.
 10. A compound of claim 1 wherein Ar is naphthyl.
 11. A compound of claim 1 wherein Ar is thienyl.
 12. A compound of claim 1 wherein Ar is thiazolyl.
 13. A compound of claim 1 wherein Ar is cyclohexenyl.
 14. A compound of claim 1 wherein Ar is an optionally substituted phenyl group of formula (2).
 15. A compound of claim 1 whereinW is CH; A is X--(CH₂)₂ --Ar; and Ar is a group of formula (2) ##STR13## wherein four of R¹⁰ to R¹⁴ are H and one of R¹⁰ to R¹⁴ is Cl, (C₁ -C₄) alkyl, halo (C₁ -C₇) alkyl, branched (C₃ -C₆) alkyl, (C₁ -C₇) alkoxy, halo (C₁ -C₇) alkoxy, phenyl, substituted phenyl, phenoxy, or substituted phenoxy.
 16. A compound of claim 15 wherein R⁴ is F.
 17. An insecticide or miticide composition comprising an insect- or mite-inactivating amount of a compound of claim 1 in combination with a phytologically-acceptable carrier.
 18. An insecticide or miticide method which comprises applying to the locus of an insect or mite an insect- or mite-inactivating amount of a compound of claim
 1. 